JPH0255117B2 - - Google Patents
Info
- Publication number
- JPH0255117B2 JPH0255117B2 JP62275627A JP27562787A JPH0255117B2 JP H0255117 B2 JPH0255117 B2 JP H0255117B2 JP 62275627 A JP62275627 A JP 62275627A JP 27562787 A JP27562787 A JP 27562787A JP H0255117 B2 JPH0255117 B2 JP H0255117B2
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- water
- peroxide
- hydrogen peroxide
- light
- 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.)
- Expired - Lifetime
Links
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 38
- 239000011941 photocatalyst Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 150000002978 peroxides Chemical class 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 238000007664 blowing Methods 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- MXCPYJZDGPQDRA-UHFFFAOYSA-N dialuminum;2-acetyloxybenzoic acid;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3].CC(=O)OC1=CC=CC=C1C(O)=O MXCPYJZDGPQDRA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- 239000005416 organic matter Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000004042 decolorization Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 4
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000010800 human waste Substances 0.000 description 3
- 239000004021 humic acid Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 238000004332 deodorization Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910017115 AlSb Inorganic materials 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
- 229910005542 GaSb Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910000673 Indium arsenide Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 239000005446 dissolved organic matter Substances 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 description 1
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Catalysts (AREA)
Description
〔産業上の利用分野〕
本発明は、各種産業廃水、都市下水、上水等の
水の処理方法に関し、水中の有機物の酸化分解処
理、脱色、脱臭、殺菌を行なう方法に関するもの
である。
表―１に本発明の用途並びに用途に対応した利
用分野を示す。
[Industrial Application Field] The present invention relates to a method for treating water such as various industrial wastewater, urban sewage, and tap water, and relates to a method for oxidative decomposition, decolorization, deodorization, and sterilization of organic matter in water. Table 1 shows the uses of the present invention and the fields of application corresponding to the uses.
水中の有機物の処理方法について説明する。
従来から、微生物を使用する方法以外の方法と
して一般に良く知られている排水中の溶解有機物
の除去方法としては、活性炭法、オゾン法、電気
分解法、化学的酸化法、電気透析法などがある。
この中、実際規模のものとして工業化されてい
るものとしては、活性炭法、オゾン法、電気分解
法の各処理法がある。
しかしながら、これらの処理法には次の如き問
題点がある。
活性炭法
処理効率は比較的良いが、活性炭の再生が面
倒でありコストが高い。
オゾン法
有機物処理として脱色、脱臭、分解作用の効
率は比較的良く、他に殺菌作用が存在するが、
オゾンは製造するのにコスト高であり、又未利
用のオゾンが廃オゾンとして放出されるため、
リーク廃オゾンの公害対策が必要である。
電気分解法
有機物処理としての脱色の効率は比較的良い
が、有機物分解には充分な効果が得られない。
又、コスト高である。
〔発明の目的〕
本発明は、水を過酸化物の存在下に光照射され
ている光触媒で処理することにより、水中の有機
物の酸化分解或いは水の脱色及び／又は脱臭処理
並びに殺菌処理を行なうことを目的とする。
〔発明の構成〕
本発明は、水をPH８以下で過酸化物の存在下に
反応装置の下部から空気又は酸素を吹込みながら
光照射されている光触媒で処理することを特徴と
する水の処理方法であつて、水の脱色、脱臭、殺
菌あるいは水に含有されている有機物の分解等を
効率よく行なうものである。
第１図に基いて本発明によりし尿を処理する方
法について説明する。
生物化学的に脱窒されたし尿は原水導入口１よ
り反応槽１０に導入され反応部Ａで酸化処理さ
れ、処理液は出口２より排出される。
反応部Ａは、浮遊状態の光触媒３及び紫外線ラ
ンプ４よりなり下部配管５より過酸化水素が配管
６より散気装置７を介して空気が供給される。
空気は反応部Ａ中を気泡となり上昇し、その撹
拌作用等により反応部Ａにおける作用を促進す
る。
反応部Ａにおいては、紫外線ランプ４の照射を
受けた光触媒３と過酸化水素の作用により原水中
の有機物が分解され、脱色とCODの除去が行な
われる。
反応部Ａにおける作用は、次のように考えられ
る。
紫外線照射を受けた光触媒と過酸化水素によ
り、非常に強力な酸化作用を有するヒドロキシラ
ジカルをはじめとする酸素活性種（例・OH，
HO2，，O2 -）が効率良く生成され、原水中の有
機物と反応し、該有機物を酸化分解する。
次に、光触媒について説明する。
光触媒材は、光照射により励起され、過酸化水
素との作用により酸素活性種を効果的に生成させ
るものであれば何れでも良い。
通常半導体材料が効果的であり容易に入手出
来、加工性も良いことから好ましい。
効果や経済性の面から、Se，Ge，Si，Ti，
Zn，Cu，Al，Sn，Ga，In，Ｐ，As，Sb，Ｃ，
Cd，Ｓ，Te，Ni，Fe，Co，Ag，Mo，Sr，Ｗ，
Cr，Ba，Pbのいずれか、又はこれらの化合物、
又は合金、又は酸化物が好ましく、これらは単独
で、又二種類以上を複合して用いる。
例えば、元素としてはSi，Ge，Se、化合物と
してはAlP，AlAs，GaP，AlSb，GaAs，InP，
GaSb，InAs，InSb，CdS，CdSe，ZnS，MoS2，
WTe2，Cr2Te3，MoTe，Cu2S，WS2、酸化物
としてはTiO2，Bi2O3，CuO，Cu2O，ZnO，
MoO3，InO3，Ag2O，PbO，SrTiO3，BaTiO3，
Co3O4，Fe2O3，NiO等がある。
光触媒は、第１図に示したように浮遊状態で用
いてもよく、或いは、壁面への固定化、膜状ある
いは膜固定した状態即ち、紫外線を透過する膜で
光触媒を包み、又は挾み込んで膜状に固定した状
態で用いてもよい。
光触媒の使用量は、一般に0.001〜５％、通常
は0.01〜１％（原水に対する重量比）である。
光触媒は、粉体状のままで用いることが出来る
が、焼結、蒸着、スパツタリング等の周知の方法
で適宜の形状にして用いることも出来る。
これらは、反応装置の規模や形状、処理対象物
の濃度、種類、光源の種類や形状、光触媒の種
類、希望する効果、経済性等により適宜選択する
ことが出来る。
過酸化物は、光触媒との作用により酸素活性種
を効率良く生成するものであれば何れでも良い。
過酸化物としては、過酢酸、過酸化水素等があ
るが、通常過酸化水素が取扱いやすさ、効果等か
ら好ましい。
光源としては、可視及び／又は紫外領域の光を
発するものであれば良く、紫外線ランプや太陽光
を適宜用いることが出来る。通常、紫外線ランプ
が処理速度が早いこと等から好ましい。
紫外線は光触媒材好ましくは光触媒材と過酸化
物の双方に吸収される波長を有するものが良く、
光触媒材、過酸化物の種類により定まる光吸収領
域の波長を放出するランプを選べば良い。例えば
光触媒材としてTiO2を用いる場合は、光吸収が
近紫外部にあるため近紫外部の波長の光を放出す
るランプを使用する。
光源は、水銀灯、水素放電管、キセノン放電
管、ライマン放電管などを適宜１種又は２種以上
を組合せて利用することが出来る。
光源が過酸化物に吸収される波長を有すること
により、過酸化物の光触媒による酸素活性種への
変換に加えて、過酸化物の紫外線吸収による自己
分解による酸素活性種の生成が起こり、酸素活性
種の生成効率が高まる。
光源の位置は、第１図に示すように光触媒反応
器１０内部に設置してもよいが、別の例として該
反応器外側に設置し紫外線を反射面を利用するこ
とにより、あるいは照射窓を通して光触媒材に照
射するようにしても良い。
過酸化水素の供給は、第１図に示すように反応
部Ａの下部に別途供給する他、処理水入口１より
供給してもよく、あるいは供給空気６に同伴させ
行なつてもよく、反応装置の規模や形状等により
適宜選択することができる。
過酸化水素の供給量は、有機物の濃度、種類、
効果、経済性等により、予め予備試験を行ない適
宜決めることが出来る。
例えば、有機物としてフミン酸が多い場合は、
フミン酸濃度に対して0.1倍〜1.0倍（過酸化水素
のフミン酸に対する重量比）、通常0.3〜0.5倍程
度の過酸化水素の濃度で十分な効果が得られる。
過酸化水素は、光触媒との作用で効率良くヒド
ロキシラジカルのような酸素活性種に変換され、
非常に強力な酸化剤として効果的に作用するの
で、供給量は比較的に少なくても良い。
反応部Ａでの撹拌混合は、第１図に示す例にお
いては供給空気の気泡により行なわれているが空
気の代わりに酸素を用いてもよい。空気又は酸素
の供給は反応部Ａでの酸化反応を促進させる。
１１は、粒状の光触媒３が反応部Ａから外部に
流出するのを妨ぐスクリーンである。
１２は、供給空気や反応により生じたCO2等の
排気孔である。
反応部Ａの温度は、温度を上昇させた方が反応
は促進されるが、一般には特に加温は不要で任意
に行なうことが出来る。
処理水のPHは８以下で実施するのが好ましい。
実施例
第１図に示した装置を用いてCOD100mg／、
色度200゜、PH約６の排水を光触媒反応器に入れ、
過酸化水素を加え下方より空気を散気孔を介して
供給し、CODと色度の変化を調べた。
反応器大きさ；３
光触媒：二酸化チタン（TiO2，アナターゼ
型）、１ｇ／
光 源：低圧水銀灯32W
過酸化水素：50mg／（100％過酸化水素換算）
空気量：500ml／min
又、光と光触媒のみの場合（過酸化水素がない
場合）及び光と過酸化水素のみの場合（光触媒が
ない場合）についても比較例として同様に行なつ
た。
結 果
第２図、第３図にそれぞれCODの経時変化及
び色度の経時変化を示す。第２図、第３図から10
分後及び40分後の値を下表に示す。
A method for treating organic matter in water will be explained. Traditionally, well-known methods for removing dissolved organic matter from wastewater other than methods using microorganisms include activated carbon method, ozone method, electrolysis method, chemical oxidation method, and electrodialysis method. . Among these, the activated carbon method, the ozone method, and the electrolysis method are the ones that have been industrialized on an actual scale. However, these processing methods have the following problems. Activated carbon method Treatment efficiency is relatively good, but regeneration of activated carbon is troublesome and costs are high. Ozone method has relatively high efficiency in decolorizing, deodorizing, and decomposing effects as an organic matter treatment, and also has bactericidal effects, but
Ozone is expensive to produce, and unused ozone is released as waste ozone.
It is necessary to take measures against pollution from leaked waste ozone. Electrolysis method The efficiency of decolorization as a treatment for organic matter is relatively good, but a sufficient effect cannot be obtained for decomposing organic matter.
Moreover, the cost is high. [Object of the invention] The present invention performs oxidative decomposition of organic matter in water, decolorization and/or deodorization treatment, and sterilization treatment of water by treating water with a photocatalyst that is irradiated with light in the presence of peroxide. The purpose is to [Structure of the Invention] The present invention is a water treatment characterized by treating water with a photocatalyst that is irradiated with light while blowing air or oxygen from the lower part of a reaction device in the presence of peroxide at a pH of 8 or less. It is a method that efficiently decolorizes, deodorizes, and sterilizes water, and decomposes organic matter contained in water. A method for treating human waste according to the present invention will be explained based on FIG. Biochemically denitrified human waste is introduced into the reaction tank 10 through the raw water inlet 1 and oxidized in the reaction section A, and the treated liquid is discharged through the outlet 2. The reaction section A includes a photocatalyst 3 in a floating state and an ultraviolet lamp 4, and hydrogen peroxide is supplied from a lower pipe 5, and air is supplied from a pipe 6 via an aeration device 7. Air rises in the form of bubbles in the reaction part A, and promotes the action in the reaction part A by its stirring action and the like. In the reaction section A, the organic matter in the raw water is decomposed by the action of the photocatalyst 3 irradiated by the ultraviolet lamp 4 and hydrogen peroxide, and decolorization and COD removal are performed. The action in the reaction part A can be considered as follows. The photocatalyst and hydrogen peroxide exposed to ultraviolet rays generate active oxygen species (e.g. OH,
HO 2 , , O 2 − ) is efficiently generated, reacts with organic matter in the raw water, and oxidizes and decomposes the organic matter. Next, the photocatalyst will be explained. The photocatalyst material may be any material as long as it is excited by light irradiation and effectively generates oxygen active species through its action with hydrogen peroxide. Generally, semiconductor materials are preferred because they are effective, readily available, and have good processability. From the viewpoint of effectiveness and economy, Se, Ge, Si, Ti,
Zn, Cu, Al, Sn, Ga, In, P, As, Sb, C,
Cd, S, Te, Ni, Fe, Co, Ag, Mo, Sr, W,
Cr, Ba, Pb or any of these compounds,
, alloys, or oxides are preferable, and these are used alone or in combination of two or more types. For example, the elements are Si, Ge, Se, and the compounds are AlP, AlAs, GaP, AlSb, GaAs, InP,
GaSb, InAs, InSb, CdS, CdSe, ZnS, MoS 2 ,
WTe 2 , Cr 2 Te 3 , MoTe, Cu 2 S, WS 2 , oxides include TiO 2 , Bi 2 O 3 , CuO, Cu 2 O, ZnO,
MoO 3 , InO 3 , Ag 2 O, PbO, SrTiO 3 , BaTiO 3 ,
Examples include Co 3 O 4 , Fe 2 O 3 , NiO, etc. The photocatalyst may be used in a floating state as shown in Figure 1, or it may be immobilized on a wall, in the form of a film, or in a membrane-fixed state, that is, it may be wrapped or sandwiched in a film that transmits ultraviolet rays. It may also be used in a state where it is fixed in the form of a film. The amount of photocatalyst used is generally 0.001 to 5%, usually 0.01 to 1% (weight ratio to raw water). The photocatalyst can be used as it is in powder form, but it can also be used in an appropriate shape by well-known methods such as sintering, vapor deposition, and sputtering. These can be appropriately selected depending on the scale and shape of the reaction apparatus, the concentration and type of the object to be treated, the type and shape of the light source, the type of photocatalyst, desired effects, economic efficiency, and the like. Any peroxide may be used as long as it can efficiently generate oxygen active species through its action with the photocatalyst. Peroxides include peracetic acid, hydrogen peroxide, etc., but hydrogen peroxide is usually preferred due to its ease of handling and effectiveness. The light source may be anything that emits light in the visible and/or ultraviolet region, and an ultraviolet lamp or sunlight can be used as appropriate. Usually, an ultraviolet lamp is preferable because of its fast processing speed. The ultraviolet rays preferably have a wavelength that is absorbed by both the photocatalytic material and the peroxide.
It is sufficient to select a lamp that emits wavelengths in the light absorption region determined by the type of photocatalyst material and peroxide. For example, when using TiO 2 as a photocatalyst material, light absorption is in the near ultraviolet range, so a lamp that emits light with a wavelength in the near ultraviolet range is used. As the light source, a mercury lamp, a hydrogen discharge tube, a xenon discharge tube, a Lyman discharge tube, etc. can be appropriately used alone or in combination of two or more types. Because the light source has a wavelength that is absorbed by peroxide, in addition to the conversion of peroxide into oxygen active species by the photocatalyst, the generation of oxygen active species occurs through self-decomposition due to ultraviolet absorption of peroxide, and oxygen The efficiency of generating active species increases. The light source may be placed inside the photocatalytic reactor 10 as shown in FIG. 1, but as another example, the light source may be placed outside the reactor and the ultraviolet rays may be emitted by using a reflective surface or through an irradiation window. The photocatalytic material may also be irradiated with the irradiation. Hydrogen peroxide may be supplied separately to the lower part of the reaction section A as shown in FIG. It can be selected as appropriate depending on the scale, shape, etc. of the device. The amount of hydrogen peroxide supplied depends on the concentration and type of organic matter,
Depending on effectiveness, economical efficiency, etc., a preliminary test can be carried out in advance to decide as appropriate. For example, if there is a lot of humic acid as an organic substance,
A sufficient effect can be obtained at a hydrogen peroxide concentration of 0.1 to 1.0 times the humic acid concentration (weight ratio of hydrogen peroxide to humic acid), usually about 0.3 to 0.5 times. Hydrogen peroxide is efficiently converted into oxygen active species such as hydroxyl radicals through the action of a photocatalyst.
Since it effectively acts as a very strong oxidizing agent, the amount supplied may be relatively small. In the example shown in FIG. 1, stirring and mixing in the reaction section A is carried out by supplying air bubbles, but oxygen may be used instead of air. The supply of air or oxygen accelerates the oxidation reaction in reaction section A. 11 is a screen that prevents the granular photocatalyst 3 from flowing out from the reaction section A. Reference numeral 12 indicates an exhaust hole for supplying air and CO 2 generated by the reaction. Although the reaction is promoted by increasing the temperature of the reaction part A, generally heating is not necessary and can be carried out as desired. It is preferable that the pH of the treated water is 8 or less. Example Using the apparatus shown in Figure 1, COD100mg/,
Put wastewater with a chromaticity of 200° and a pH of about 6 into a photocatalytic reactor,
Hydrogen peroxide was added and air was supplied from below through the diffuser hole, and changes in COD and chromaticity were examined. Reactor size: 3 Photocatalyst: Titanium dioxide (TiO 2 , anatase type), 1g/Light source: Low pressure mercury lamp 32W Hydrogen peroxide: 50mg/(100% hydrogen peroxide conversion) Air volume: 500ml/min Also, light and Comparative examples were also carried out in the case of only a photocatalyst (in the absence of hydrogen peroxide) and in the case of only light and hydrogen peroxide (in the absence of a photocatalyst). Results Figures 2 and 3 show the changes in COD and chromaticity over time, respectively. 10 from Figures 2 and 3
The values after 1 minute and 40 minutes are shown in the table below.
１ 光、光触媒及び過酸化物を用いることによ
り、
酸素活性種が効果的に生成し、水中汚染物
の処理が効果的に行なえる。
有機物は、酸化分解し、分解生成物はCO2
のような気体状となるので、分解処理後の溶
液の後処理が不要である。
処理液の温度、あるいはPH等の管理が不要
で、測置の維持管理が容易である。
処理工程が簡素化され、取扱いやすく経済
的に有利となつた。
従えば、従来のし尿処理におけるCOD除去及
び脱色工程は混合槽、凝集槽、凝集沈でん槽、オ
ゾン反応槽、砂ろ過槽、活性炭槽等から成り複雑
で、コスト高である。
２ 光と光触媒を用いることにより、過酸化物は
効率良く、ヒドロキシラジカルのような強力な
酸素活性種を生成するので、過酸化物の供給量
は比較的少なくても効果がある。
1. By using light, photocatalysts, and peroxides, active oxygen species can be effectively generated and water pollutants can be effectively treated. Organic matter is decomposed by oxidation, and the decomposition product is CO 2
Since it is in a gaseous state, post-treatment of the solution after the decomposition treatment is not necessary. There is no need to manage the temperature or pH of the processing liquid, and the maintenance and management of the measurement system is easy. The processing process has been simplified, making it easier to handle and economically advantageous. Accordingly, the COD removal and decolorization process in conventional human waste treatment is complicated and expensive, as it consists of a mixing tank, a flocculation tank, a flocculation sedimentation tank, an ozone reaction tank, a sand filter tank, an activated carbon tank, etc. 2. By using light and a photocatalyst, peroxide efficiently generates strong oxygen active species such as hydroxyl radicals, so even a relatively small amount of peroxide is effective.
第１図は本発明方法を説明するための概略図、
第２図及び第３図は、本発明方法ならびに光と光
触媒のみ及び光と過酸化水素のみを用いた場合の
COD及び色度の経時変化を示す図である。
１…被処理水入口、２…処理水出口、３…光触
媒、４…紫外線ランプ、５…過酸化水素供給管、
６…空気供給管、９…気泡、１０…反応器、１１
…スクリーン、１２…排気孔。
FIG. 1 is a schematic diagram for explaining the method of the present invention,
Figures 2 and 3 show the results of the present invention, using only light and a photocatalyst, and using only light and hydrogen peroxide.
FIG. 3 is a diagram showing changes in COD and chromaticity over time. 1... Inlet of water to be treated, 2... Outlet of treated water, 3... Photocatalyst, 4... Ultraviolet lamp, 5... Hydrogen peroxide supply pipe,
6...Air supply pipe, 9...Bubble, 10...Reactor, 11
...Screen, 12...Exhaust hole.
Claims (1)
置の下部から空気又は酸素を吹込みながら光照射
されている光触媒で処理することを特徴とする光
触媒による水の処理方法。 ２ 光触媒が半導体である特許請求の範囲第１項
記載の水の処理方法。 ３ 光触媒がSe，Ge，Si，Ti，Zn，Cu，Sn，
Al，Ga，In，Ｐ，As，Bb，Ｃ，Cd，Ｓ，Te，
Ni，Fe，Co，Ag，Mo，Sr，Ｗ，Cr，Ba，Pb
のいずれか、又はその化合物、又は合金、又は酸
化物より選ばれた一種又は二種以上の複合体より
なる特許請求の範囲第２項記載の水の処理方法。 ４ 過酸化物が過酸化水素である特許請求の範囲
第１項、第２項又は第３項記載の水の処理方法。 ５ 光触媒への光の照射を水銀灯、水素放電管、
キセノン放電管またはライマン放電管を用いて行
なう特許請求の範囲第１項乃至第４項の何れか１
つに記載の水の処理方法。[Claims] 1. Water using a photocatalyst, which is characterized in that water is treated with a photocatalyst that is irradiated with light while blowing air or oxygen from the bottom of a reaction device in the presence of peroxide at a pH of 8 or less. Processing method. 2. The water treatment method according to claim 1, wherein the photocatalyst is a semiconductor. 3 The photocatalyst is Se, Ge, Si, Ti, Zn, Cu, Sn,
Al, Ga, In, P, As, Bb, C, Cd, S, Te,
Ni, Fe, Co, Ag, Mo, Sr, W, Cr, Ba, Pb
The water treatment method according to claim 2, comprising a composite of one or more selected from the group consisting of any one of the above, or a compound, an alloy, or an oxide thereof. 4. The water treatment method according to claim 1, 2 or 3, wherein the peroxide is hydrogen peroxide. 5 Irradiation of light to the photocatalyst using a mercury lamp, hydrogen discharge tube,
Any one of claims 1 to 4, which is carried out using a xenon discharge tube or a Lyman discharge tube.
The water treatment method described in .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27562787A JPH01119394A (en) | 1987-11-02 | 1987-11-02 | Treatment of water by photocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27562787A JPH01119394A (en) | 1987-11-02 | 1987-11-02 | Treatment of water by photocatalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01119394A JPH01119394A (en) | 1989-05-11 |
| JPH0255117B2 true JPH0255117B2 (en) | 1990-11-26 |
Family
ID=17558090
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27562787A Granted JPH01119394A (en) | 1987-11-02 | 1987-11-02 | Treatment of water by photocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01119394A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MD4041C2 (en) * | 2008-11-10 | 2010-12-31 | Государственный Университет Молд0 | Process for biochemical treatment of vinasse |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1147771A (en) * | 1997-07-31 | 1999-02-23 | Meidensha Corp | Continuous water passing type water treatment apparatus |
| KR100297928B1 (en) * | 1999-03-09 | 2001-09-22 | 이정형 | Method of nitrogen removal in wastewater with photocatalytic technology |
| JP4191373B2 (en) * | 2000-09-01 | 2008-12-03 | 独立行政法人科学技術振興機構 | Method for producing highly active photocatalyst and method for treating hydrogen sulfide for recovering hydrogen gas with low energy using highly active photocatalyst |
| WO2003037504A1 (en) * | 2001-11-02 | 2003-05-08 | Japan Techno Co., Ltd. | Vibratory stirrer for sterilization and sterilizer and sterilization method employing vibratory stirrer |
| JP2006068604A (en) * | 2004-08-31 | 2006-03-16 | Toyota Motor Corp | Deodorizing device |
| JP4881308B2 (en) * | 2005-08-08 | 2012-02-22 | ヤーマン株式会社 | Spraying equipment |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6354992A (en) * | 1986-08-27 | 1988-03-09 | Oji Paper Co Ltd | Photochemical treatment of pulp waste water |
| JPH0194998A (en) * | 1987-10-05 | 1989-04-13 | Agency Of Ind Science & Technol | Photochemical treatment of waste water |
-
1987
- 1987-11-02 JP JP27562787A patent/JPH01119394A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6354992A (en) * | 1986-08-27 | 1988-03-09 | Oji Paper Co Ltd | Photochemical treatment of pulp waste water |
| JPH0194998A (en) * | 1987-10-05 | 1989-04-13 | Agency Of Ind Science & Technol | Photochemical treatment of waste water |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MD4041C2 (en) * | 2008-11-10 | 2010-12-31 | Государственный Университет Молд0 | Process for biochemical treatment of vinasse |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01119394A (en) | 1989-05-11 |
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