JPH11262759A - Water-treatment apparatus using photocatalyst and method therefor - Google Patents
Water-treatment apparatus using photocatalyst and method thereforInfo
- Publication number
- JPH11262759A JPH11262759A JP10068512A JP6851298A JPH11262759A JP H11262759 A JPH11262759 A JP H11262759A JP 10068512 A JP10068512 A JP 10068512A JP 6851298 A JP6851298 A JP 6851298A JP H11262759 A JPH11262759 A JP H11262759A
- Authority
- JP
- Japan
- Prior art keywords
- water
- photocatalyst
- treated
- treatment apparatus
- water treatment
- 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.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 120
- 238000000034 method Methods 0.000 title description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 85
- 239000007789 gas Substances 0.000 claims abstract description 51
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000001301 oxygen Substances 0.000 claims abstract description 34
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 230000001678 irradiating effect Effects 0.000 claims abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 32
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 30
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 21
- 238000002347 injection Methods 0.000 claims description 18
- 239000007924 injection Substances 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 239000010419 fine particle Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 abstract description 28
- 241000894006 Bacteria Species 0.000 abstract description 13
- 244000005700 microbiome Species 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 4
- 239000010409 thin film Substances 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 229910001882 dioxygen Inorganic materials 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 230000002093 peripheral effect Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- 239000002759 woven fabric Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000008235 industrial water Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000011882 ultra-fine particle Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 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
- 239000010408 film Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000003206 sterilizing agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、産業廃水、生活
排水、飲料水、プール水、浴槽水、冷却水、洗浄水、貯
留水などの水処理装置および水処理方法に関し、さらに
詳しくは光触媒を用いた高度な水処理装置および水処理
方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water treatment apparatus and a water treatment method for industrial wastewater, domestic wastewater, drinking water, pool water, bathtub water, cooling water, washing water, storage water, and the like. The present invention relates to an advanced water treatment apparatus and a water treatment method used.
【０００２】[0002]
【従来の技術】半導体物質である酸化チタン等の光触媒
に波長が４００ｎｍ以下の紫外光が照射されると、価電
子帯に正孔が発生するとともに伝導帯に電子が生じる。
この正孔の酸化電位は、フッ素、オゾン、過酸化水素等
の酸化電位よりも高く、有機物は光触媒により完全に酸
化分解されて最終的には二酸化炭素ガスと水、硫酸、硝
酸などに完全酸化される。光触媒による酸化反応のメカ
ニズムは、まだ十分に解明されていないが、光触媒に紫
外光が照射された際に生じる正孔またはこの正孔と水が
反応して生じる極めて反応活性に富むヒドロオキシルラ
ジカル（ＯＨラジカル）により、完全酸化反応が起こる
と考えられている。この際、照射された際に生じる正孔
と同時に発生する電子と酸素ガス等との還元反応が並行
して進行する。2. Description of the Related Art When a photocatalyst such as titanium oxide as a semiconductor substance is irradiated with ultraviolet light having a wavelength of 400 nm or less, holes are generated in a valence band and electrons are generated in a conduction band.
The oxidation potential of these holes is higher than the oxidation potential of fluorine, ozone, hydrogen peroxide, etc., and organic substances are completely oxidized and decomposed by a photocatalyst, and finally are completely oxidized to carbon dioxide gas and water, sulfuric acid, nitric acid, etc. Is done. The mechanism of the oxidation reaction by the photocatalyst has not been fully elucidated yet, but a hole generated when the photocatalyst is irradiated with ultraviolet light or a highly reactive hydroxyl radical generated by a reaction between the hole and water ( OH radical) is believed to cause a complete oxidation reaction. At this time, a reduction reaction between electrons generated simultaneously with holes generated upon irradiation and oxygen gas or the like proceeds in parallel.
【０００３】光触媒の作用は、このような強力な酸化反
応にとどまらず、従来のオゾンや過酸化水素、塩素等の
殺菌剤よりも強い殺菌能力を有するという特徴がある。
また、光照射により生じた正孔やＯＨラジカルの寿命は
ミリ秒以下と短いので、オゾンや過酸化水素等の酸化剤
のように処理後に残留がなく、残留酸化剤を処理する装
置が不要であるという利点がある。このようなことか
ら、これまでに光触媒を用いた多くの水処理装置が考案
されている（例えば、特公昭６２−１９２４０号公報、
特公昭６３−４９５４０号公報、特開平２−２５１２４
１号公報など）。[0003] The action of the photocatalyst is not limited to such a strong oxidation reaction, but is characterized by having a sterilizing ability stronger than conventional sterilizing agents such as ozone, hydrogen peroxide and chlorine.
In addition, since the lifetime of holes and OH radicals generated by light irradiation is as short as milliseconds or less, there is no residue after treatment such as an oxidizing agent such as ozone or hydrogen peroxide, and a device for treating the residual oxidizing agent is unnecessary. There is an advantage that there is. For this reason, many water treatment apparatuses using a photocatalyst have been devised (for example, Japanese Patent Publication No. 62-19240,
JP-B-63-49540, JP-A-2-25124
No. 1).
【０００４】しかしながら、光触媒による作用は光が照
射される光触媒表面のみで起こるため、効率良く処理を
行うには光触媒の表面積を大きくして被処理水との接触
効率を高める必要がある。また、光触媒に紫外光が照射
された際に生じる正孔またはＯＨラジカルは寿命が短い
ので短時間で反応させる必要がある。また、紫外光は水
に吸収されやすく、水中で減衰しやすいという問題があ
る。However, since the action of the photocatalyst occurs only on the surface of the photocatalyst irradiated with light, it is necessary to increase the surface area of the photocatalyst to increase the contact efficiency with the water to be treated in order to perform the treatment efficiently. In addition, holes or OH radicals generated when the photocatalyst is irradiated with ultraviolet light have a short life, and therefore need to be reacted in a short time. Further, there is a problem that ultraviolet light is easily absorbed by water and is easily attenuated in water.
【０００５】このような問題を解決するために、例えば
特開平８−４７６８７号公報において、図７の構成図に
示すような装置が考案されている。本従来例では、酸化
チタンを塗布したガラス玉（径が数ｍｍ〜数ｃｍで光透
過率６５％）からなる光触媒体７２が固定床光触媒反応
器７０に充填され、光触媒の表面積を大きくして被処理
水との接触効率を高めている。７１は波長域が３００〜
４００ｎｍの紫外線ランプ（ブラックライト）、７３は
送液ポンプである。光触媒体７２の充填層の厚みは照射
する光の進行方向に５０ｍｍとされ、固定床光触媒反応
器７０の内壁面には光反射用のミラーが張られている。In order to solve such a problem, for example, Japanese Patent Application Laid-Open No. 8-47687 has devised an apparatus as shown in the configuration diagram of FIG. In this conventional example, a fixed-bed photocatalyst reactor 70 is filled with a photocatalyst 72 composed of glass balls (diameter of several mm to several cm and light transmittance of 65%) coated with titanium oxide to increase the surface area of the photocatalyst. The contact efficiency with the water to be treated is increased. 71 has a wavelength range of 300 to
A 400 nm ultraviolet lamp (black light) 73 is a liquid sending pump. The thickness of the packed layer of the photocatalyst body 72 is 50 mm in the traveling direction of the irradiated light, and a mirror for reflecting light is provided on the inner wall surface of the fixed-bed photocatalytic reactor 70.
【０００６】次に動作について説明する。固定床光触媒
反応器７０の内部に設けられた紫外線ランプ７１が点灯
されたのち、送液ポンプ７３により被処理水が固定床光
触媒反応器７０に送られ、紫外光が照射された光触媒体
７２により被処理水の脱臭、殺菌および有機物の除去が
行われる。Next, the operation will be described. After the ultraviolet lamp 71 provided inside the fixed-bed photocatalyst reactor 70 is turned on, the water to be treated is sent to the fixed-bed photocatalyst reactor 70 by the liquid feed pump 73, and the photocatalyst 72 irradiated with ultraviolet light. Deodorization, sterilization, and removal of organic substances of the water to be treated are performed.
【０００７】また、特開平８−８９７２５号公報におい
て、図８（ａ）の構成図および図８（ｂ）の断面図に示
すような装置が考案されている。本従来例では、石英ガ
ラス管からなる反応容器８５の水の流路８３に光触媒
（酸化チタン）が表面に溶射された多孔体の網８４が設
けられている。８０は殺菌手段、８１は光源である紫外
線ランプ、８２は紫外線ランプ８１の光が透過可能な
壁、８６は紫外線ランプ８１の光を反射する光反射板、
８７は入口、８８は出口である。矢印は紫外線光を示
す。８９は網８４の孔を示す。In Japanese Patent Application Laid-Open No. 8-89725, an apparatus as shown in the configuration diagram of FIG. 8A and the cross-sectional view of FIG. 8B has been devised. In this conventional example, a porous net 84 having a surface sprayed with a photocatalyst (titanium oxide) is provided in a water channel 83 of a reaction vessel 85 made of a quartz glass tube. 80 is a sterilizing means, 81 is an ultraviolet lamp as a light source, 82 is a wall through which the light of the ultraviolet lamp 81 can pass, 86 is a light reflecting plate that reflects the light of the ultraviolet lamp 81,
87 is an entrance and 88 is an exit. Arrows indicate ultraviolet light. Reference numeral 89 denotes a hole in the net 84.
【０００８】次に動作について示す。細菌が存在する水
が入口８７から入り、網８４の隙間を通って出口８８か
ら出るときに、紫外線ランプ８１から放射された紫外線
は網８４に照射される。一方、網８４の孔８９を貫通し
た紫外線は反応容器８５の内面に構成された鏡８６で反
射され、その反射光は網８４に照射される。それぞれ紫
外線が照射された光触媒の表面においては酸化還元作用
が行なわれる結果、反応容器８５の流路８３を流れる水
の細菌が殺菌される。また、特開平９−１５５３３７号
公報においては、図９の構成図に示すように、光反応ユ
ニット９１の外管９４の入口９５に導かれた被処理水が
酸化チタン光触媒を構成する酸化チタン被覆ガラス繊維
織布９３の間隙を縫ってかつ内管９２を構成する紫外線
ランプからの紫外線を浴びつつ出口側に流通するように
構成されている。本従来例では外管９４の径は５０ｍ
ｍ、内管９２の径は３４ｍｍ、酸化チタン被覆ガラス繊
維織布９３の厚さは０．２〜０．６ｍｍとされている。Next, the operation will be described. When water containing bacteria enters from the inlet 87 and exits from the outlet 88 through the gap of the net 84, the ultraviolet rays emitted from the ultraviolet lamp 81 are irradiated on the net 84. On the other hand, the ultraviolet light that has passed through the hole 89 of the net 84 is reflected by a mirror 86 formed on the inner surface of the reaction vessel 85, and the reflected light is applied to the net 84. As a result of the oxidation-reduction action being performed on the surface of the photocatalyst irradiated with the ultraviolet light, bacteria of the water flowing through the channel 83 of the reaction vessel 85 are sterilized. In addition, in Japanese Patent Application Laid-Open No. 9-155337, as shown in the configuration diagram of FIG. 9, the water to be treated guided to the inlet 95 of the outer tube 94 of the photoreaction unit 91 is coated with titanium oxide constituting the titanium oxide photocatalyst. It is configured to sew the gap between the glass fiber woven fabrics 93 and circulate to the outlet side while being exposed to the ultraviolet rays from the ultraviolet lamp constituting the inner tube 92. In this conventional example, the diameter of the outer tube 94 is 50 m.
m, the diameter of the inner tube 92 is 34 mm, and the thickness of the glass fiber woven fabric 93 coated with titanium oxide is 0.2 to 0.6 mm.
【０００９】[0009]
【発明が解決しようとする課題】図７に示す特開平８−
４７６８７号公報における固定床光触媒反応器７０にお
いては、紫外線ランプ７１から照射された光の大部分は
紫外線ランプ７１のごく近傍にある光触媒体７２にのみ
吸収され、全体の光触媒体７２に紫外光が照射されない
ため、十分な浄化効果が得られないという問題があっ
た。そこで、光の進行方向に対する光触媒体７２の充填
層の厚みをさらに薄くすることが容易に考えられるが、
反応器７０に光触媒体７２が密に充填された場合、反応
器７０の空隙率が極めて小さく、処理水量を大きくする
ことができないという問題がある。また、反応表面積を
大きくするために、微小の粉体状に形成した光触媒材を
被処理水に混合することが考えられるが、粉体状の光触
媒材と処理水を分離するのは極めて困難で装置が複雑に
なるという問題がある。SUMMARY OF THE INVENTION FIG.
In the fixed-bed photocatalyst reactor 70 in JP 47687, most of the light emitted from the ultraviolet lamp 71 is absorbed only by the photocatalyst 72 very close to the ultraviolet lamp 71, and the entire photocatalyst 72 receives ultraviolet light. Since irradiation is not performed, there is a problem that a sufficient purification effect cannot be obtained. Therefore, it is easy to further reduce the thickness of the packed layer of the photocatalyst body 72 in the light traveling direction.
When the photocatalyst body 72 is densely filled in the reactor 70, there is a problem that the porosity of the reactor 70 is extremely small and the amount of treated water cannot be increased. In order to increase the reaction surface area, it is conceivable to mix a photocatalyst material formed in a fine powder form with the water to be treated, but it is extremely difficult to separate the powdery photocatalyst material from the treated water. There is a problem that the device becomes complicated.
【００１０】また、図８に示す特開平８−８９７２５号
公報においては、酸化および殺菌作用は紫外線が照射さ
れた光触媒の表面のみで起こり、酸化チタン等の光触媒
が表面に溶射された多孔体の網８４の表面に接触するご
く一部の被処理水のみしか処理されないという問題があ
る。また、紫外光は水に吸収されやすいため、紫外線ラ
ンプ８１から照射された紫外光は殺菌手段８０の内部に
設けた多孔体の網８４に照射される前に減衰し、効率が
悪く効果が十分でないという問題があった。In Japanese Patent Application Laid-Open No. Hei 8-89725 shown in FIG. 8, the oxidizing and germicidal actions occur only on the surface of the photocatalyst irradiated with ultraviolet rays, and the surface of the porous body is sprayed with a photocatalyst such as titanium oxide. There is a problem that only a small part of the water to be treated that comes into contact with the surface of the net 84 is treated. Further, since ultraviolet light is easily absorbed by water, the ultraviolet light emitted from the ultraviolet lamp 81 is attenuated before being applied to the porous net 84 provided inside the sterilizing means 80, so that the efficiency is poor and the effect is insufficient. There was a problem that was not.
【００１１】また、特開平９−１５５３３７号公報の構
成においても、厚さは０．２〜０．６ｍｍ程度の酸化チ
タン被覆ガラス繊維織布９３の間隙を流れる被処理水は
処理されるが、酸化チタン被覆ガラス繊維織布９３と内
管９２の間を流れる被処理水を処理することができない
という問題があった。In the configuration of Japanese Patent Application Laid-Open No. 9-155337, water to be treated flowing through the gap between the titanium oxide-coated glass fiber woven fabric 93 having a thickness of about 0.2 to 0.6 mm is treated. There is a problem that the water to be treated flowing between the titanium oxide-coated glass fiber woven fabric 93 and the inner tube 92 cannot be treated.
【００１２】本発明は上記のような問題点を解消するた
めになされたもので、光触媒と被処理水が接触する反応
部において、強力な混合攪拌作用を生じさせて、被処理
水を光触媒に効率良く接触させると共に十分な酸素を供
給し、被処理水に含まれる有害有機物、細菌等の微生
物、臭気物質や難分解物質などを効率良く分解除去する
高度な水処理装置および水処理方法を得ることを目的と
する。また、多量の被処理水を簡易に処理できる工業的
な水処理装置および水処理方法を得ることを目的とす
る。The present invention has been made in order to solve the above-mentioned problems. In the reaction section where the photocatalyst and the water to be treated come into contact with each other, a strong mixing and stirring action is caused to convert the water to be treated into the photocatalyst. An advanced water treatment apparatus and method for efficiently contacting and supplying sufficient oxygen to efficiently decompose and remove harmful organic substances, microorganisms such as bacteria, odorous substances, hardly decomposable substances, etc. contained in the water to be treated are obtained. The purpose is to: Another object of the present invention is to provide an industrial water treatment apparatus and a water treatment method capable of easily treating a large amount of water to be treated.
【００１３】[0013]
【課題を解決するための手段】本発明に係る光触媒を用
いた水処理装置は、上記の目的を達成するために、被処
理水を噴射する噴射口と、酸素含有気体を吸引する気体
吸引口と、噴射された被処理水と吸引された気体を混合
攪拌する反応部と、この反応部の表面に光の照射により
正孔と電子を発生する光触媒を有する光反応面、この光
反応面に光を照射する光源とを設けたものである。In order to achieve the above object, a water treatment apparatus using a photocatalyst according to the present invention is provided with an injection port for injecting water to be treated and a gas suction port for sucking oxygen-containing gas. And a reaction section for mixing and agitating the injected water to be treated and the sucked gas, and a photoreaction surface having a photocatalyst for generating holes and electrons by irradiating light to the surface of the reaction section. And a light source for irradiating light.
【００１４】また本発明に係る光触媒を用いた水処理装
置は、反応部における圧力損失を抑えるために、被処理
水の流れ方向に対して断面積を段階的に大きくした反応
部を設けたものであっても良い。Further, the water treatment apparatus using a photocatalyst according to the present invention is provided with a reaction section having a cross-sectional area which is increased stepwise in the flow direction of the water to be treated in order to suppress a pressure loss in the reaction section. It may be.
【００１５】また本発明に係る光触媒を用いた水処理装
置は、反応部の表面の光触媒が酸化チタン、酸化亜鉛な
どの金属酸化物を含むものであっても良い。[0015] In the water treatment apparatus using a photocatalyst according to the present invention, the photocatalyst on the surface of the reaction section may contain a metal oxide such as titanium oxide or zinc oxide.
【００１６】また、この発明に係る光触媒を用いた水処
理装置は、光触媒の光吸収効率を高めるために、マンガ
ン、ニッケル、銅、クロム、鉄などの微粒子を更に添加
したものであっても良い。Further, the water treatment apparatus using a photocatalyst according to the present invention may further include fine particles of manganese, nickel, copper, chromium, iron or the like in order to increase the light absorption efficiency of the photocatalyst. .
【００１７】また本発明に係る光触媒を用いた水処理装
置は、さらに光触媒の反応効果を高めるために、反応部
の表面の光触媒が上記金属酸化物または上記微粒子を添
加した金属酸化物にゼオライト、アルミナ、活性炭など
の多孔質材料を更に添加したものであっても良い。Further, in the water treatment apparatus using a photocatalyst according to the present invention, in order to further enhance the reaction effect of the photocatalyst, the photocatalyst on the surface of the reaction part is made of zeolite, A porous material such as alumina or activated carbon may be further added.
【００１８】また本発明に係る光触媒を用いた水処理装
置は、反応部において被処理水と光触媒との接触面積を
高めるために、反応部の内部に酸化チタンなどの光触媒
を塗布した網を設けたものであっても良い。In the water treatment apparatus using a photocatalyst according to the present invention, a net coated with a photocatalyst such as titanium oxide is provided inside the reaction section in order to increase the contact area between the water to be treated and the photocatalyst in the reaction section. May be used.
【００１９】また本発明に係る光触媒を用いた水処理装
置は、電子の還元反応を高めるとともに、光触媒の反応
負荷を小さくするために、気体吸引口から酸化剤のオゾ
ンを含有した気体を供給させるようにしたものであって
も良い。Further, in the water treatment apparatus using a photocatalyst according to the present invention, a gas containing an oxidant, ozone, is supplied from a gas suction port in order to enhance the reduction reaction of electrons and reduce the reaction load of the photocatalyst. Such a configuration may be used.
【００２０】この発明に係る光触媒を用いた水処理方法
は、被処理水を噴射し、これに酸素含有気体またはオゾ
ン含有気体を吸引させ攪拌混合する工程と、攪拌混合し
た被処理水と気体とを光の照射により正孔と電子を発生
する光触媒に接触させる工程とを備えたものである。The water treatment method using a photocatalyst according to the present invention comprises the steps of injecting water to be treated, sucking an oxygen-containing gas or an ozone-containing gas into the water, stirring and mixing the water, and mixing the water and the gas with stirring and mixing. In contact with a photocatalyst that generates holes and electrons by light irradiation.
【００２１】[0021]
【発明の実施の形態】実施の形態１．以下、本発明の実
施例を図にもとづいて説明する。図１は、本発明の水処
理装置の一実施の形態を示す縦断面図で、図２は図１の
ｉ−ｉ′線断面図である。図１および図２において、１
０は本発明に係る水処理装置、１１は被処理水、１２は
被処理水を高速で噴射する噴射口、１３は石英管または
ガラス管等からなる反応管、１３ａは反応管１３の内周
面に塗布された酸化チタン（ＴｉＯ2 など）等の光触媒
の薄膜、１４は紫外線ランプ等の光源、１４ａは光源１
４を収納するランプ室、１４ｂはランプ室１４ａの外周
面で光反射材からなる。１５は処理水の流速を徐々に減
速するディフューザ、１６は処理水、１７は空気または
酸素ガス、１８は空気または酸素ガス１７を吸引する気
体吸引口、１９は被処理水入口、２０は出口である。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiment 1 Hereinafter, embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a longitudinal sectional view showing an embodiment of the water treatment apparatus of the present invention, and FIG. 2 is a sectional view taken along the line ii 'of FIG. In FIGS. 1 and 2, 1
Reference numeral 0 denotes a water treatment apparatus according to the present invention, 11 denotes water to be treated, 12 denotes an injection port for jetting the water to be treated at a high speed, 13 denotes a reaction tube formed of a quartz tube or a glass tube, and 13a denotes an inner periphery of the reaction tube 13. A thin film of a photocatalyst such as titanium oxide (TiO 2 or the like) applied to the surface, 14 a light source such as an ultraviolet lamp, and 14 a a light source 1
The lamp chamber 14b for accommodating 4 is made of a light reflecting material on the outer peripheral surface of the lamp chamber 14a. Reference numeral 15 denotes a diffuser for gradually reducing the flow rate of the treated water, 16 denotes treated water, 17 denotes air or oxygen gas, 18 denotes a gas suction port for sucking air or oxygen gas 17, 19 denotes an inlet of the water to be treated, and 20 denotes an outlet. is there.
【００２２】次に、動作について説明する。被処理水１
１は送水ポンプにより加圧されて、水処理装置１０の被
処理水入口１９に導かれて噴射口１２に供給され、噴射
口１２から高速で噴射されたのち、反応管１３に導かれ
る。被処理水１１が噴射口１２から高速で噴射されると
同時に、気体吸引口１８から酸素含有気体が吸引されて
反応管１３に導かれ、噴射口１２から高速で噴射された
被処理水１１と強力に混合される。上記反応管１３にお
いて、被処理水１１は光触媒の薄膜１３ａにより処理さ
れて処理水１６となって、ディフューザ１５を通って出
口２０から流出する。この際、反応管１３において高い
混合攪拌作用を維持するには、反応管１３の内径を噴射
口１２の内径の１．２倍から２．５倍程度とするのが好
ましい。Next, the operation will be described. Treated water 1
1 is pressurized by a water pump, guided to a treated water inlet 19 of the water treatment apparatus 10, supplied to the injection port 12, injected from the injection port 12 at a high speed, and then guided to the reaction tube 13. At the same time as the water to be treated 11 is injected at high speed from the injection port 12, the oxygen-containing gas is sucked from the gas suction port 18 and guided to the reaction tube 13, and the water to be treated 11 is injected at high speed from the injection port 12. Strongly mixed. In the reaction tube 13, the water to be treated 11 is treated by the photocatalytic thin film 13 a to become treated water 16, and flows out of the outlet 20 through the diffuser 15. At this time, in order to maintain a high mixing and stirring action in the reaction tube 13, the inner diameter of the reaction tube 13 is preferably about 1.2 to 2.5 times the inner diameter of the injection port 12.
【００２３】このように、本発明による反応管１３にお
いては、噴射口１２から高速で噴射された被処理水１１
と気体吸引口１８から吸引された酸素含有気体の混合に
より強力な攪拌作用が発生し、被処理水１１を酸化チタ
ン等の光触媒の薄膜１３ａの表面に効率良く接触できる
とともに十分な酸素が供給され、電子と酸素との還元反
応が並行して進行し、正孔と電子が再結合することが無
く、光触媒と被処理水との反応が効率良く行われる。な
お、気体吸引口１８から流入される空気または酸素ガス
１７は、フィルター等により空気中の細菌または微粒子
が除去されたのち、反応管１３に導かれる。また、噴射
口１２から噴射される被処理水１１の流速は、送水ポン
プ１７の動力を出来るだけ少なくし、かつ光触媒の反応
性を高めるために、数ｍ／秒から数１０ｍ／秒とするの
が好ましい。As described above, in the reaction tube 13 according to the present invention, the water to be treated 11 injected at a high speed from the injection port 12 is provided.
A strong stirring action is generated by the mixing of the oxygen-containing gas sucked from the gas suction port 18 with the gas suction port 18, so that the water 11 to be treated can be efficiently brought into contact with the surface of the thin film 13a of the photocatalyst such as titanium oxide, and sufficient oxygen is supplied. The reduction reaction between electrons and oxygen proceeds in parallel, and holes and electrons do not recombine, so that the reaction between the photocatalyst and the water to be treated is performed efficiently. The air or oxygen gas 17 flowing from the gas suction port 18 is guided to the reaction tube 13 after bacteria or fine particles in the air are removed by a filter or the like. In addition, the flow rate of the water to be treated 11 injected from the injection port 12 is set to several m / sec to several tens m / sec in order to reduce the power of the water pump 17 as much as possible and to increase the reactivity of the photocatalyst. Is preferred.
【００２４】また、反応管１３の長さについても、送水
ポンプ１７の動力を出来るだけ少なくし、かつ光触媒の
反応性を高めるために、反応管１３の内径の数倍から数
１０倍程度にするのが好ましい。また、気体吸引口１８
から流入される空気または酸素ガス１７の流量は、被処
理水１１の容積流量の１／１０〜１／１００程度で十分
な攪拌効果と酸素供給が可能である。The length of the reaction tube 13 is also set to several times to several tens times the inner diameter of the reaction tube 13 in order to reduce the power of the water pump 17 as much as possible and to enhance the reactivity of the photocatalyst. Is preferred. The gas suction port 18
The flow rate of the air or oxygen gas 17 flowing from the water is about 1/10 to 1/100 of the volume flow rate of the water 11 to be treated, and a sufficient stirring effect and oxygen supply are possible.
【００２５】なお、被処理水１１の水量が多い場合で
も、本発明においては噴射口１２の内径および反応管１
３の内径をそれぞれ定められた流速になるように容易に
大きくすることができ、簡易に工業的な水処理装置を実
現することができる。In the present invention, even when the amount of the water to be treated 11 is large, the inner diameter of the injection port 12 and the
The inner diameter of the pipe 3 can be easily increased so as to have a predetermined flow rate, and an industrial water treatment apparatus can be easily realized.
【００２６】上記の反応管１３の内周面には、酸化チタ
ン等の光触媒の薄膜１３ａが塗布されており、被処理水
１１が反応管１３に導かれるとランプ室１４ａに設置さ
れた紫外線ランプ等の光源１４が点灯され、反応管１３
の内周面に塗布された酸化チタン等の光触媒の薄膜１３
ａに紫外光が照射される。本発明では紫外光が反応管１
３の外部から照射されるので、反応管１３内での紫外光
の損失はない。The inner peripheral surface of the reaction tube 13 is coated with a thin film 13a of a photocatalyst such as titanium oxide. When the water 11 to be treated is introduced into the reaction tube 13, an ultraviolet lamp installed in a lamp chamber 14a is provided. Is turned on, and the reaction tube 13 is turned on.
Thin film 13 of photocatalyst such as titanium oxide applied to the inner peripheral surface of
a is irradiated with ultraviolet light. In the present invention, the ultraviolet light is applied to the reaction tube 1.
Since irradiation is performed from the outside of the reaction tube 3, there is no loss of ultraviolet light in the reaction tube 13.
【００２７】酸化チタン等の光触媒の薄膜１３ａに４１
０ｎｍ以下の紫外光が照射されると、酸化チタンの価電
子帯に正孔が生じるとともに伝導帯に電子が発生し、発
生した正孔は水と迅速に反応して強力な酸化力を有する
ヒドロオキシルラジカル（ＯＨラジカル）を生じる。こ
のようにして、酸化チタン薄膜１３ａの表面に生成した
正孔またはＯＨラジカルが被処理水１１に含まれる有害
有機物または細菌等の微生物や臭気物質と反応して、有
害有機物または臭気物質は二酸化炭素ガスと水に分解さ
れ、細菌等の微生物は殺菌される。The thin film 13a of a photocatalyst such as titanium oxide
When irradiated with ultraviolet light of 0 nm or less, holes are generated in the valence band of titanium oxide and electrons are generated in the conduction band, and the generated holes quickly react with water to form a hydro- oxidant having strong oxidizing power. This produces oxyl radicals (OH radicals). In this manner, the holes or OH radicals generated on the surface of the titanium oxide thin film 13a react with harmful organic substances or microorganisms such as bacteria contained in the water to be treated 11 or odor substances, and the harmful organic substances or odor substances become carbon dioxide. It is broken down into gas and water, and microorganisms such as bacteria are killed.
【００２８】この際、非常に活性な正孔またはＯＨラジ
カルと被処理水１１に含まれる有害な有機物または細菌
等の微生物の反応速度は、極めて速く数ミリ秒以内で反
応が完了するため、被処理水の有害有機物などが除去さ
れる量は紫外線ランプ１４の照射量に律速される。一
方、紫外光照射時に正孔と同時に生成した電子は、酸素
と迅速に反応してスーパーオキサイド（Ｏ2 - ）が生成
する。このとき、酸素が不足すると未反応の電子が正孔
と再結合し、正孔の酸化反応を阻害することになるが、
本発明では十分な酸素含有気体が光触媒表面に供給され
るので、上記のような電子と正孔の再結合を防止でき、
その結果、被処理水１１と酸化チタン等の光触媒の薄膜
１３ａの酸化反応効率を高めることができる。At this time, the reaction rate between extremely active holes or OH radicals and harmful organic substances or microorganisms such as bacteria contained in the water to be treated 11 is extremely fast, and the reaction is completed within several milliseconds. The amount by which harmful organic substances and the like in the treated water are removed is limited by the irradiation amount of the ultraviolet lamp 14. On the other hand, electrons generated at the same time as holes upon irradiation with ultraviolet light quickly react with oxygen to generate superoxide (O 2 − ). At this time, if oxygen is insufficient, unreacted electrons are recombined with holes, which hinders the oxidation reaction of holes.
In the present invention, a sufficient oxygen-containing gas is supplied to the photocatalyst surface, so that recombination of electrons and holes as described above can be prevented,
As a result, the efficiency of the oxidation reaction between the water to be treated 11 and the thin film 13a of the photocatalyst such as titanium oxide can be increased.
【００２９】以上のように、本発明によれば、反応管１
３における強力な混合攪拌効果により、被処理水１１を
酸化チタン等の光触媒の薄膜１３ａの表面に効率良く接
触できるとともに十分な酸素が供給され、酸化チタン等
の光触媒の薄膜１３ａと被処理水１１との反応効率を飛
躍的に高めることができる。As described above, according to the present invention, the reaction tube 1
3, the water to be treated 11 can be efficiently brought into contact with the surface of the thin film 13a of the photocatalyst such as titanium oxide and sufficient oxygen is supplied, and the thin film 13a of the photocatalyst such as titanium oxide and the water 11 The reaction efficiency of the reaction can be dramatically improved.
【００３０】上記反応管１３の内周面に塗布する光触媒
薄膜１３ａの厚さは、被処理水１１に含まれる有機物濃
度や光源１４の照射強度などにより異なるが、０．１μ
ｍ（マイクロメータ）〜数１０μｍが好ましい。反応管
１３の厚さは、数ｍｍ程度で、紫外光を良く透過する石
英ガラスが望ましいが、通常のガラス（例えば硬質ガラ
ス）であってもよい。光源１４は、酸化チタン等の光触
媒が正孔および電子を効率良く生じさせる紫外光（波長
が４１０ｎｍ以下）を多く含むことが望ましく、紫外線
ランプや低圧または高圧水銀ランプ、または３００〜４
００ｎｍの波長をもつ蛍光ランプなどであってよい。The thickness of the photocatalyst thin film 13a applied to the inner peripheral surface of the reaction tube 13 varies depending on the concentration of organic substances contained in the water 11 to be treated, the irradiation intensity of the light source 14, and the like.
m (micrometer) to several tens of μm are preferred. The thickness of the reaction tube 13 is about several millimeters, and is desirably quartz glass that transmits ultraviolet light well, but may be ordinary glass (for example, hard glass). The light source 14 desirably includes a large amount of ultraviolet light (wavelength of 410 nm or less) that allows a photocatalyst such as titanium oxide to efficiently generate holes and electrons, and includes an ultraviolet lamp, a low-pressure or high-pressure mercury lamp, or 300 to 4
A fluorescent lamp having a wavelength of 00 nm may be used.
【００３１】この実施の形態においては、内表面に光触
媒膜を塗布した反応部において、噴射口から高速で噴射
された被処理水と酸素含有気体を混合させることによ
り、強力な混合攪拌作用を生じさせるため、被処理水を
光触媒に効率良く接触させるとともに十分な酸素が供給
でき、被処理水に含まれる有害有機物、細菌等の微生
物、臭気物質や難分解物質などを効率良くかつ高度に分
解除去できる。また、反応部に光触媒体が充填されない
ため、多量の水を処理でき、光触媒による工業的な高度
水処理装置が得られる。また、光触媒に紫外光が照射さ
れる反応部へ酸素含有ガスが供給され、光触媒による酸
化還元反応を効率良く進行させることができ、反応効率
の高い光触媒による水処理装置が得られる。In this embodiment, a strong mixing and stirring effect is produced by mixing the water to be treated injected at a high speed from the injection port with the oxygen-containing gas in the reaction section having the photocatalytic film coated on the inner surface. In this way, the water to be treated can be efficiently brought into contact with the photocatalyst and sufficient oxygen can be supplied, and harmful organic substances, microorganisms such as bacteria, odorous substances and hardly decomposable substances contained in the water to be treated are efficiently and highly decomposed and removed. it can. Further, since the reaction section is not filled with the photocatalyst, a large amount of water can be treated, and an industrial advanced water treatment apparatus using a photocatalyst can be obtained. Further, the oxygen-containing gas is supplied to the reaction section where the photocatalyst is irradiated with ultraviolet light, so that the redox reaction by the photocatalyst can proceed efficiently, and a water treatment apparatus using the photocatalyst with high reaction efficiency can be obtained.
【００３２】実施の形態２．また、上記の実施の形態１
では、反応管１３が直管の場合について説明したが、被
処理水１１が反応管１３を通過する際の圧力損失を小さ
くするために、図３に示したように、被処理水１１の流
れ方向に対して反応管１３の径を段階的に大きくしても
よい。図３（ａ）および（ｂ）は縦断面図で、図３
（ａ）は被処理水１１の流れ方向に対して反応管１３の
径を例えば１０％程度毎に段階的に大きくしたもので、
図３（ｂ）は反応管１３の径をテーパー状に連続的に大
きくし、例えば反応管１３の出口の径を入口の径の１０
％〜３０％程度大きくしたものである。Embodiment 2 FIG. Further, the first embodiment described above
In the above, the case where the reaction tube 13 is a straight tube has been described. However, in order to reduce the pressure loss when the water to be treated 11 passes through the reaction tube 13, as shown in FIG. The diameter of the reaction tube 13 may be increased stepwise in the direction. 3A and 3B are longitudinal sectional views, and FIG.
(A) is a diagram in which the diameter of the reaction tube 13 is increased stepwise, for example, about every 10% with respect to the flow direction of the water 11 to be treated.
FIG. 3B shows that the diameter of the reaction tube 13 is continuously increased in a tapered shape.
% To about 30%.
【００３３】実施の形態３．次に、図４は、本発明の他
の実施の形態を示す縦断面図で、図１の反応管１３にお
いて、被処理水と光触媒の接触面積を大きくするように
したものである。図５は図４のｉ−ｉ′線に沿った断面
図である。図において、１０は本発明に係る水処理装
置、４１は酸化チタン等の光触媒が表面に溶射された円
筒状の網、４２は円筒状の網４１の孔である。Embodiment 3 Next, FIG. 4 is a longitudinal sectional view showing another embodiment of the present invention, in which the contact area between the water to be treated and the photocatalyst is increased in the reaction tube 13 of FIG. FIG. 5 is a sectional view taken along line ii 'of FIG. In the figure, 10 is a water treatment apparatus according to the present invention, 41 is a cylindrical net having a photocatalyst such as titanium oxide sprayed on its surface, and 42 is a hole of the cylindrical net 41.
【００３４】図４および図５において、反応管１３の内
部に酸化チタン等の光触媒が表面に溶射された円筒状の
網４１を設け、被処理水１１と光触媒の反応面積を大き
くすることにより、反応効率を高めることができる。こ
の際、円筒状の網４１は被処理水１１の流れ方向に対し
て反応管１３の先端から数ｍｍから数ｃｍ離し、かつ光
照射方向に対して反応管１３から数ｍｍ内部に設置する
のが好ましい。なお、円筒状の網４１は耐腐食性のチタ
ン合金やステンレス等の金属金網または高分子樹脂の網
であってよい。また、光触媒の薄膜１３ａは網の表面に
形成したものでも良い。4 and 5, a cylindrical net 41 having a surface coated with a photocatalyst such as titanium oxide is provided inside the reaction tube 13 to increase the reaction area between the water 11 to be treated and the photocatalyst. Reaction efficiency can be increased. At this time, the cylindrical net 41 is set at a distance of several mm to several cm from the tip of the reaction tube 13 with respect to the flow direction of the water 11 to be treated, and is set inside the reaction tube 13 with respect to the light irradiation direction. Is preferred. The cylindrical net 41 may be a metal net such as a corrosion-resistant titanium alloy or stainless steel, or a net made of a polymer resin. Further, the thin film 13a of the photocatalyst may be formed on the surface of the net.
【００３５】実施の形態４．次に、図６は本発明に係る
水処理装置を適用した水処理のフローを示す説明図で、
１０は本発明に係る水処理装置、６１は被処理水、６２
は水槽、６３は循環ポンプである。なお、本発明に係る
水処理装置１０の内部構成は図１と同様である。Embodiment 4 FIG. Next, FIG. 6 is an explanatory diagram showing a flow of water treatment to which the water treatment device according to the present invention is applied.
10 is a water treatment apparatus according to the present invention, 61 is water to be treated, 62
Is a water tank and 63 is a circulation pump. The internal configuration of the water treatment device 10 according to the present invention is the same as that of FIG.
【００３６】次に、動作について説明する。紫外線ラン
プ１４が点灯されたのち、被処理水６１が循環ポンプ６
３により加圧されて本発明に係る水処理装置１０に導か
れる。そして、水処理装置１０の反応管１３において、
噴射口１２から高速で噴射された被処理水６１が気体吸
引口１８から吸引された酸素含有気体と混合されながら
光触媒により処理され、水槽６２に戻される。このよう
な循環動作を繰り返し、反応管１３において紫外光が照
射された酸化チタン薄膜１３ａの表面に被処理水６１が
効率良く接触し、被処理水６１に含まれる有害な有機物
または細菌等の微生物や臭気物質が効率良く除去され
る。Next, the operation will be described. After the ultraviolet lamp 14 is turned on, the water 61 to be treated is
3 and is guided to the water treatment apparatus 10 according to the present invention. Then, in the reaction tube 13 of the water treatment device 10,
The water to be treated 61 injected at a high speed from the injection port 12 is treated by the photocatalyst while being mixed with the oxygen-containing gas sucked from the gas suction port 18 and returned to the water tank 62. By repeating such a circulating operation, the water 61 to be treated efficiently contacts the surface of the titanium oxide thin film 13a irradiated with ultraviolet light in the reaction tube 13, and harmful organic substances or microorganisms such as bacteria contained in the water 61 to be treated. And odor substances are efficiently removed.
【００３７】この際、気体吸引口１８から吸引する空気
の供給流量１７は容積比で被処理水１１の流量の約１／
２０とし、噴射口１２から噴射される被処理水６１の流
速は約１０ｍ／ｓ、また反応管１３の径は噴射口１２の
径の約１．５倍とした。なお、循環ポンプ６３は揚程が
数ｍで運転された。At this time, the supply flow rate 17 of the air sucked from the gas suction port 18 is about 1 / the volume rate of the water 11 to be treated.
The flow rate of the water to be treated 61 injected from the injection port 12 was about 10 m / s, and the diameter of the reaction tube 13 was about 1.5 times the diameter of the injection port 12. The circulation pump 63 was operated at a head of several meters.
【００３８】図６において、本発明の効果を実証するた
めに、モデル難分解性有機物として約５０ｐｐｍ（ｍｇ
／ｌ）の酢酸（ＣＨ3 ＣＯＯＨ）を含んだ被処理水（３
０ｌ）の分解実験を行った。その結果、難分解性有機物
である酢酸は迅速に分解して二酸化炭素と水に分解され
た。この際、被処理水６１に含まれる酢酸を９０％除去
するのに必要な時間は、紫外線ランプ本数（照射電力）
を同一にして、別途上記と同様に光触媒薄膜１３ａが塗
布された反応管１３に、直接に上記と同量の被処理水６
１を供給した場合と比較すると、約１／２に短縮され
た。In FIG. 6, in order to demonstrate the effect of the present invention, about 50 ppm (mg
/ L) acetic acid (CH 3 COOH)
0l). As a result, acetic acid, a hardly decomposable organic substance, was rapidly decomposed into carbon dioxide and water. At this time, the time required to remove 90% of acetic acid contained in the water to be treated 61 is determined by the number of ultraviolet lamps (irradiation power).
And the same amount of water 6 to be treated is directly supplied to the reaction tube 13 coated with the photocatalytic thin film 13a in the same manner as described above.
Compared with the case where 1 was supplied, the time was reduced to about 1/2.
【００３９】循環ポンプ６３の動力は被処理水６１を噴
射せずに直接反応管１３に供給した場合の方が少なくて
よいが、紫外線ランプの電力が大きく、全体の電力は本
発明による方がかなり少なくてよい。このように、本発
明によれば、水槽６２の被処理水６１を短時間にかつ省
電力にて処理できる。The power of the circulating pump 63 may be smaller when the water 61 to be treated is directly supplied to the reaction tube 13 without jetting it. However, the electric power of the ultraviolet lamp is large, and the total electric power according to the present invention is smaller. It may be quite small. As described above, according to the present invention, the water 61 to be treated in the water tank 62 can be treated in a short time and with low power consumption.
【００４０】実施の形態５．上記の各実施の形態では、
光触媒として酸化チタン（ＴｉＯ２など）を用いた例を
示したが、実験結果によると、酸化亜鉛などの金属酸化
物でも酸化チタンとほぼ同様な効果が得られた。また、
これらの金属酸化物の光触媒に０．１％〜１％程度の少
量のマンガン、ニッケル、銅、クロム、鉄などの超微粒
子（０．１ナノメータから数ナノメータ）を添加する
と、紫外光または可視光の吸収効率を数１０％高めるこ
とができた。また、上記金属酸化物または上記超微粒子
を添加した金属酸化物にゼオライト、アルミナ、活性炭
などの多孔質材料を数％から数１０％添加した光触媒を
用いると、さらに処理時間が短縮された。Embodiment 5 In each of the above embodiments,
Although an example using titanium oxide (TiO2 or the like) as a photocatalyst was shown, according to the experimental results, almost the same effect as titanium oxide was obtained even with a metal oxide such as zinc oxide. Also,
When ultra-fine particles (0.1 to several nanometers) of manganese, nickel, copper, chromium, iron or the like are added in a small amount of about 0.1% to 1% to the photocatalyst of these metal oxides, ultraviolet light or visible light can be obtained. Was improved by several tens of percent. Further, when a photocatalyst in which a porous material such as zeolite, alumina, and activated carbon was added to the metal oxide or the metal oxide to which the ultrafine particles were added was used, the processing time was further reduced.
【００４１】実施の形態６．また、酸素含有気体１７に
少量のアルゴンガスを添加すると、電子と酸素の反応が
さらに活性化され、被処理水と酸化チタンの反応効率が
より高まることがわかった。Embodiment 6 FIG. It was also found that when a small amount of argon gas was added to the oxygen-containing gas 17, the reaction between electrons and oxygen was further activated, and the reaction efficiency between the water to be treated and titanium oxide was further increased.
【００４２】また、上記の酸素含有気体１７のかわりに
オゾン含有気体（オゾンと空気、オゾンと酸素、オゾン
と空気と酸素）を供給すると、電子は酸素よりも酸化性
の高いオゾンと良く反応する。また、オゾン自身は酸化
剤であり、オゾンにより被処理水６１に含まれる有害有
機物または細菌等の微生物の一部または大部分を除去で
き、オゾンよりも強い酸化力をもつ正孔またはＯＨラジ
カルの負荷を小さくできるため、光触媒の反応負荷を小
さくでき、効率的に高度な水処理が可能となる。着色し
た被処理水をオゾンで処理すると色が消えて紫外光が通
過し易くなる効果もある。この際、反応管１３を被処理
水の流れ方向に対して複数に分割し、前段階でオゾン処
理したのち、引き続き光触媒により処理するように構成
すると、オゾンをより効果的に作用させることができ
る。When an ozone-containing gas (ozone and air, ozone and oxygen, ozone and air and oxygen) is supplied instead of the oxygen-containing gas 17, the electrons react well with ozone having a higher oxidizing property than oxygen. . In addition, ozone itself is an oxidizing agent, and can remove a part or most of microorganisms such as harmful organic substances or bacteria contained in the water 61 to be treated by ozone, and generate holes or OH radicals having a stronger oxidizing power than ozone. Since the load can be reduced, the reaction load of the photocatalyst can be reduced, and advanced water treatment can be efficiently performed. When the colored water to be treated is treated with ozone, there is also an effect that the color disappears and ultraviolet light easily passes. At this time, if the reaction tube 13 is divided into a plurality of parts in the flow direction of the water to be treated, the ozone treatment is performed in the previous stage, and then the treatment is performed by the photocatalyst, the ozone can be made to act more effectively. .
【００４３】[0043]
【発明の効果】この発明に係る光触媒を用いた水処理装
置によれば、被処理水を噴射させる噴射口、酸素含有気
体を吸引する吸引口、内周面に光の照射により正孔と電
子を発生する光触媒を有する反応部、この反応部の表面
に光を照射する光源を備えるようにしたので、被処理水
と酸素含有気体の混合による強力な混合攪拌効果が得ら
れ、被処理水に含まれる有害有機物、細菌、臭気物質、
難分解有機物などを光触媒表面に効率良く接触させるこ
とができ、短時間に高度な水処理を行える。また、本発
明においては、多量の水を処理する場合は噴射口および
反応管を大きくすればよく、簡易に光触媒による工業的
な水処理装置が得られる。また、本発明においては、光
触媒に光が照射される反応部へ酸素含有気体が供給さ
れ、光触媒による酸化還元反応を効率良く進行させるこ
とができ、反応効率の高い光触媒による水処理装置が得
られる。According to the water treatment apparatus using the photocatalyst according to the present invention, the injection port for injecting the water to be treated, the suction port for sucking the oxygen-containing gas, and the holes and the electrons formed by irradiating the inner peripheral surface with light. A reaction section having a photocatalyst that generates a light, and a light source for irradiating light to the surface of the reaction section is provided, so that a strong mixing and stirring effect by mixing the water to be treated and the oxygen-containing gas is obtained, and Harmful organic substances, bacteria, odor substances,
Refractory organic substances can be efficiently brought into contact with the photocatalyst surface, and advanced water treatment can be performed in a short time. In the present invention, when treating a large amount of water, the injection port and the reaction tube may be enlarged, and an industrial water treatment apparatus using a photocatalyst can be easily obtained. Further, in the present invention, the oxygen-containing gas is supplied to the reaction section where light is irradiated to the photocatalyst, the oxidation-reduction reaction by the photocatalyst can proceed efficiently, and a water treatment apparatus using the photocatalyst with high reaction efficiency can be obtained. .
【００４４】また、反応部の断面積を被処理水の流れ方
向に対して段階的に大きくすれば、反応部における圧力
損失を抑えることができる。If the cross-sectional area of the reaction section is increased stepwise with respect to the flow direction of the water to be treated, the pressure loss in the reaction section can be suppressed.
【００４５】また、光触媒が酸化チタン、酸化亜鉛の少
なくとも一つを含む場合には、光照射により発生した正
孔により被処理水中の物質の分解および殺菌を行うこと
ができる。When the photocatalyst contains at least one of titanium oxide and zinc oxide, the substances generated in the water to be treated can be decomposed and sterilized by holes generated by light irradiation.
【００４６】また、光触媒が、マンガン、ニッケル、
銅、クロムおよび鉄の少なくとも一つの微粒子を更に含
む場合には、光触媒の光吸収効率を高めることが出来
る。The photocatalyst is composed of manganese, nickel,
When at least one fine particle of copper, chromium and iron is further included, the light absorption efficiency of the photocatalyst can be increased.
【００４７】また、光触媒が、ゼオライト、アルミナお
よび活性炭の少なくとも一つを更に含む場合は、光触媒
の反応効率を高めることができる。When the photocatalyst further contains at least one of zeolite, alumina and activated carbon, the reaction efficiency of the photocatalyst can be increased.
【００４８】また、反応部に光触媒を塗布した網を設け
れば、被処理水と光触媒との接触面積を高めることがで
きる。If a net coated with a photocatalyst is provided in the reaction section, the contact area between the water to be treated and the photocatalyst can be increased.
【００４９】また、気体吸収口からオゾン含有気体を供
給するようにすれば、電子の還元反応を高めるとともに
光触媒の反応負荷を小さくできる。When an ozone-containing gas is supplied from the gas absorption port, the reduction reaction of electrons can be enhanced and the reaction load of the photocatalyst can be reduced.
【００５０】この発明に係る光触媒を用いた水処理方法
は、被処理水を噴射し、これに酸素含有気体またはオゾ
ン含有気体を吸引させ攪拌混合する工程と、攪拌混合し
た被処理水と気体を光の照射により正孔と電子を発生す
る光触媒に接触させる工程とを備えたので、被処理水と
酸素含有気体またはオゾン含有気体が良く攪拌混合さ
れ、被処理水を光触媒に効率良く接触させると共に十分
な酸素を供給し、被処理水に含まれる有害有機物、細菌
等の微生物、臭気物質や難分解物質などを効率良く分解
除去することができる。The water treatment method using a photocatalyst according to the present invention comprises the steps of injecting the water to be treated, sucking an oxygen-containing gas or an ozone-containing gas into the water, stirring and mixing, and mixing the water and the gas with stirring and mixing. Contacting with a photocatalyst that generates holes and electrons by light irradiation, so that the water to be treated and the oxygen-containing gas or ozone-containing gas are well stirred and mixed, and the water to be treated is efficiently brought into contact with the photocatalyst. By supplying sufficient oxygen, it is possible to efficiently decompose and remove harmful organic substances, microorganisms such as bacteria, odor substances, hardly decomposable substances and the like contained in the water to be treated.
【図１】 この発明に係る光触媒を用いた水処理装置の
一実施の形態を示す断面図である。FIG. 1 is a sectional view showing an embodiment of a water treatment apparatus using a photocatalyst according to the present invention.
【図２】 図１のｉ−ｉ′線に沿った断面図である。FIG. 2 is a cross-sectional view taken along line ii ′ of FIG.
【図３】 この発明に係る光触媒を用いた水処理装置の
他の実施の形態を示す断面図である。FIG. 3 is a sectional view showing another embodiment of the water treatment apparatus using the photocatalyst according to the present invention.
【図４】 この発明に係る光触媒を用いた水処理装置の
他の実施の形態を示す断面図である。FIG. 4 is a sectional view showing another embodiment of the water treatment apparatus using the photocatalyst according to the present invention.
【図５】 図４のｉ−ｉ′線に沿った断面図である。FIG. 5 is a sectional view taken along line ii ′ of FIG. 4;
【図６】 この発明に係る光触媒を用いた水処理装置を
用いた水処理のフローの説明図である。FIG. 6 is an explanatory diagram of a flow of water treatment using a water treatment device using a photocatalyst according to the present invention.
【図７】 従来の水処理装置の一例を示す構成図であ
る。FIG. 7 is a configuration diagram illustrating an example of a conventional water treatment apparatus.
【図８】 従来の水処理装置の他の一例を示す構成図で
ある。FIG. 8 is a configuration diagram showing another example of a conventional water treatment apparatus.
【図９】 従来の水処理装置の他の一例を示す構成図で
ある。FIG. 9 is a configuration diagram showing another example of a conventional water treatment apparatus.
１０ 水処理装置、１１ 被処理水、１２ 被処理水の
噴射口、１３ 反応管、１３ａ 光触媒の薄膜、１４
光源、１５ ディフューザ、１６ 処理水、１７ 酸素
含有気体、１８ 気体吸引口、１９ 被処理水入口、２
０ 出口、４１光触媒が表面に溶射された円筒状の網、
４２ 網孔Reference Signs List 10 water treatment device, 11 treated water, 12 treated water injection port, 13 reaction tube, 13a thin film of photocatalyst, 14
Light source, 15 diffuser, 16 treated water, 17 oxygen-containing gas, 18 gas suction port, 19 treated water inlet, 2
0 outlet, 41 cylindrical mesh with photocatalyst sprayed on the surface,
42 net hole
Claims (8)
気体を吸引する気体吸引口と、噴射された被処理水と吸
引された酸素含有気体とを混合する反応部と、この反応
部の表面に光の照射により正孔と電子を発生する光触媒
を有する光反応面と、この光反応面に光を照射する光源
とを備えた光触媒を用いた水処理装置。1. An injection port for injecting water to be treated, a gas suction port for sucking oxygen-containing gas, a reaction section for mixing the injected water to be treated and the sucked oxygen-containing gas, and the reaction section A water treatment apparatus using a photocatalyst, comprising: a photoreaction surface having a photocatalyst that generates holes and electrons by irradiating light to the surface of the surface; and a light source that irradiates the photoreaction surface with light.
対して段階的に大きくした請求項１に記載の光触媒を用
いた水処理装置。2. The water treatment apparatus using a photocatalyst according to claim 1, wherein the cross-sectional area of the reaction section is increased stepwise in the flow direction of the water to be treated.
なくとも一つを含む請求項１に記載の光触媒を用いた水
処理装置。3. The water treatment apparatus using a photocatalyst according to claim 1, wherein the photocatalyst contains at least one of titanium oxide and zinc oxide.
ムおよび鉄の少なくとも一つの微粒子を更に含む請求項
３記載の光触媒を用いた水処理装置。4. The water treatment apparatus using a photocatalyst according to claim 3, wherein the photocatalyst further includes at least one fine particle of manganese, nickel, copper, chromium, and iron.
性炭の少なくとも一つを更に含む請求項３または請求項
４記載の光触媒を用いた水処理装置。5. The water treatment apparatus using a photocatalyst according to claim 3, wherein the photocatalyst further includes at least one of zeolite, alumina, and activated carbon.
けた請求項１記載の光触媒を用いた水処理装置。6. The water treatment apparatus using a photocatalyst according to claim 1, wherein a net coated with a photocatalyst is provided inside the reaction section.
る請求項１記載の光触媒を用いた水処理装置。7. The water treatment apparatus using a photocatalyst according to claim 1, wherein an ozone-containing gas is supplied from a gas suction port.
またはオゾン含有気体を吸引させ攪拌混合する工程と、
攪拌混合した被処理水と気体を光の照射により正孔と電
子を発生する光触媒に接触させる工程とを備えた光触媒
を用いた水処理方法。8. A step of injecting the water to be treated, sucking an oxygen-containing gas or an ozone-containing gas into the water, and mixing with stirring.
Contacting the agitated and mixed water to be treated and the gas with a photocatalyst that generates holes and electrons by light irradiation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06851298A JP3646509B2 (en) | 1998-03-18 | 1998-03-18 | Water treatment equipment using photocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06851298A JP3646509B2 (en) | 1998-03-18 | 1998-03-18 | Water treatment equipment using photocatalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11262759A true JPH11262759A (en) | 1999-09-28 |
| JP3646509B2 JP3646509B2 (en) | 2005-05-11 |
Family
ID=13375854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06851298A Expired - Fee Related JP3646509B2 (en) | 1998-03-18 | 1998-03-18 | Water treatment equipment using photocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3646509B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001198584A (en) * | 1999-11-08 | 2001-07-24 | Kanagawa Acad Of Sci & Technol | Method and device for removing material having steroid skeleton |
| JP2002079068A (en) * | 2000-09-11 | 2002-03-19 | Mikio Kobayashi | Apparatus for dispersing gas-liquid mixed fluid |
| KR100386168B1 (en) * | 2000-08-31 | 2003-06-02 | (주)엔코코 | Clean water processing system |
| JP2004154742A (en) * | 2002-11-08 | 2004-06-03 | Masao Tsuchiya | Water treatment apparatus and water treatment method |
| JP2013208538A (en) * | 2012-03-30 | 2013-10-10 | Fujico Co Ltd | Hydroxyl radical water producing apparatus |
| CN103449639A (en) * | 2013-09-16 | 2013-12-18 | 中国海洋石油总公司 | Micro-series-wound-internal circulating photoelectric catalysis oxidation wastewater treatment method |
| CN110662719A (en) * | 2017-07-12 | 2020-01-07 | 首尔伟傲世有限公司 | Fluid treatment device |
| CN114620797A (en) * | 2017-07-12 | 2022-06-14 | 首尔伟傲世有限公司 | Fluid treatment device |
| CN114873709A (en) * | 2022-04-26 | 2022-08-09 | 南京万瑞环境科技有限公司 | UV gas tank |
-
1998
- 1998-03-18 JP JP06851298A patent/JP3646509B2/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001198584A (en) * | 1999-11-08 | 2001-07-24 | Kanagawa Acad Of Sci & Technol | Method and device for removing material having steroid skeleton |
| JP4588175B2 (en) * | 1999-11-08 | 2010-11-24 | 財団法人神奈川科学技術アカデミー | Method of inactivating hormone activity of female hormones with steroid skeleton |
| KR100386168B1 (en) * | 2000-08-31 | 2003-06-02 | (주)엔코코 | Clean water processing system |
| JP2002079068A (en) * | 2000-09-11 | 2002-03-19 | Mikio Kobayashi | Apparatus for dispersing gas-liquid mixed fluid |
| JP2004154742A (en) * | 2002-11-08 | 2004-06-03 | Masao Tsuchiya | Water treatment apparatus and water treatment method |
| JP2013208538A (en) * | 2012-03-30 | 2013-10-10 | Fujico Co Ltd | Hydroxyl radical water producing apparatus |
| CN103449639A (en) * | 2013-09-16 | 2013-12-18 | 中国海洋石油总公司 | Micro-series-wound-internal circulating photoelectric catalysis oxidation wastewater treatment method |
| CN103449639B (en) * | 2013-09-16 | 2014-11-05 | 中国海洋石油总公司 | Micro-series-wound-internal circulating photoelectric catalysis oxidation wastewater treatment method |
| CN110662719A (en) * | 2017-07-12 | 2020-01-07 | 首尔伟傲世有限公司 | Fluid treatment device |
| CN111039348A (en) * | 2017-07-12 | 2020-04-21 | 首尔伟傲世有限公司 | Fluid treatment device |
| CN114620797A (en) * | 2017-07-12 | 2022-06-14 | 首尔伟傲世有限公司 | Fluid treatment device |
| CN114873709A (en) * | 2022-04-26 | 2022-08-09 | 南京万瑞环境科技有限公司 | UV gas tank |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3646509B2 (en) | 2005-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101440406B1 (en) | Fluid depurator and fluid depuration method | |
| Kurukutla et al. | Sonochemical degradation of rhodamine b using oxidants, hydrogen peroxide/peroxydisulfate/peroxymonosulfate, with Fe2+ ion: proposed pathway and kinetics | |
| KR100797027B1 (en) | Apparatus for wastewater treatment by using ultraviolet light and oxidative species produced in dielectric barrier discharge tube, and method of wastewater treatment using this | |
| KR100581746B1 (en) | System for treating water | |
| JP5015542B2 (en) | Water purification equipment | |
| JP3646509B2 (en) | Water treatment equipment using photocatalyst | |
| JP3858326B2 (en) | Accelerated oxidation treatment equipment using ozone and photocatalyst | |
| Shajeelammal et al. | Treatment of real time textile effluent containing azo reactive dyes via ozonation, modified pulsed low frequency ultrasound cavitation, and integrated reactor | |
| JPH1133567A (en) | Ozone decomposing method and apparatus | |
| JP2010046611A (en) | Ultraviolet oxidation apparatus | |
| JP2010069353A (en) | Cleaning apparatus | |
| JP4229363B2 (en) | Water treatment equipment | |
| KR102052039B1 (en) | Apparatus for purifying water based on electro-peroxone reaction | |
| JP5802483B2 (en) | Water treatment apparatus for plating process and water treatment method for plating process | |
| JPH11226587A (en) | Water treatment apparatus | |
| KR101004777B1 (en) | Water treatment method and apparatus using microwave and oxidant | |
| JP4093409B2 (en) | Fluid purification method and fluid purification device | |
| JP2003285085A (en) | Water cleaning apparatus and water cleaning method | |
| KR20020094870A (en) | Advanced water and wastewater treatment apparatus and method | |
| JP2006281005A (en) | Apparatus and method for treating water using photocatalyst | |
| JPH01119394A (en) | Treatment of water by photocatalyst | |
| JPH11244873A (en) | Photocatalyst reactor | |
| JP2004267974A (en) | Apparatus for continuously oxidizing organic material | |
| JP5496629B2 (en) | Organic substance decomposition apparatus and organic substance decomposition method in pure water | |
| JP2000254667A (en) | Water treating device using photocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| RD01 | Notification of change of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7421 Effective date: 20040628 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20040827 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20041026 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20041209 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20050118 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20050131 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080218 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090218 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100218 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100218 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110218 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120218 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130218 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130218 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140218 Year of fee payment: 9 |
|
| LAPS | Cancellation because of no payment of annual fees |