JPH05337469A - Photcatalytic treatment of waste water - Google Patents
Photcatalytic treatment of waste waterInfo
- Publication number
- JPH05337469A JPH05337469A JP4173863A JP17386392A JPH05337469A JP H05337469 A JPH05337469 A JP H05337469A JP 4173863 A JP4173863 A JP 4173863A JP 17386392 A JP17386392 A JP 17386392A JP H05337469 A JPH05337469 A JP H05337469A
- Authority
- JP
- Japan
- Prior art keywords
- waste water
- wastewater
- semiconductor
- light
- 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
- 239000002351 wastewater Substances 0.000 title claims abstract description 33
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004065 semiconductor Substances 0.000 claims abstract description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000000460 chlorine Substances 0.000 claims abstract description 6
- 230000001678 irradiating effect Effects 0.000 claims abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 6
- 238000004065 wastewater treatment Methods 0.000 claims description 6
- 238000005273 aeration Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 239000010408 film Substances 0.000 claims 1
- 239000010409 thin film Substances 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 3
- 239000001569 carbon dioxide Substances 0.000 abstract description 3
- 239000011521 glass Substances 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 14
- 230000001699 photocatalysis Effects 0.000 description 8
- 239000000575 pesticide Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ZNOLGFHPUIJIMJ-UHFFFAOYSA-N fenitrothion Chemical compound COP(=S)(OC)OC1=CC=C([N+]([O-])=O)C(C)=C1 ZNOLGFHPUIJIMJ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、酸化法により前処理し
た廃水を、半導体光触媒法によって処理して分解効率を
著しく高めた廃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 wastewater treatment method in which wastewater pretreated by an oxidation method is treated by a semiconductor photocatalytic method to remarkably improve the decomposition efficiency.
【０００２】[0002]
【従来の技術】光触媒としての半導体物質の存在下に光
照射により廃水を処理する方法が知られている（例え
ば、特開昭６３−５４９９２号）。この方法では低分子
化合物は比較的短時間に炭酸ガスにまで酸化分解される
が、芳香族等の分子量の大きい化合物は、通常、中間分
解物の段階に止まり、完全処理にいたるには非常に長時
間の光照射が必要である。このために、光照射に要する
コストが大きい。またオゾン処理等の酸化法も従来から
行われているが、長時間の処理が必要であり、しかも多
くの場合に完全処理が困難である。2. Description of the Related Art There is known a method of treating wastewater by light irradiation in the presence of a semiconductor material as a photocatalyst (for example, JP-A-63-54992). In this method, low molecular weight compounds are oxidatively decomposed to carbon dioxide gas in a relatively short time.However, compounds with large molecular weight such as aromatic compounds usually stop at the intermediate decomposition product stage and are extremely difficult to reach complete treatment. Light irradiation for a long time is necessary. For this reason, the cost required for light irradiation is high. Oxidation methods such as ozone treatment have been conventionally performed, but they require long-time treatment, and in many cases, complete treatment is difficult.
【０００３】[0003]
【発明が解決しようとする課題】したがって本発明は、
光照射時間が短く、しかも有害物質を完全分解して、炭
酸ガスその他の無機物に変換することのできる廃水処理
方法を提供することを目的とする。Therefore, the present invention is
An object of the present invention is to provide a wastewater treatment method capable of converting a carbon dioxide gas and other inorganic substances by completely decomposing harmful substances with a short light irradiation time.
【０００４】[0004]
【課題を解決するための手段】本発明者らは上記の従来
の光触媒廃水処理法の難点を克服するため鋭意研究を重
ねた結果、前処理として所定の酸化処理を行ったもの
を、半導体触媒存在下に光照射することにより、有害物
質の分解効率を著しく高めうることを見い出し、この知
見に基づき本発明をなすに至った。すなわち本発明は、
廃水を酸化処理したのち、半導体触媒の存在下で光照射
して有害物質を分解処理することを特徴とする廃水処理
方法、を提供するものである。Means for Solving the Problems As a result of intensive studies conducted by the present inventors to overcome the above-mentioned drawbacks of the conventional photocatalytic wastewater treatment method, a semiconductor catalyst which has been subjected to a predetermined oxidation treatment as a pretreatment is used. It was found that the efficiency of decomposing harmful substances can be significantly increased by irradiating with light in the presence, and the present invention has been completed based on this finding. That is, the present invention is
The present invention provides a method for treating wastewater, which comprises oxidizing the wastewater and then irradiating it in the presence of a semiconductor catalyst to decompose harmful substances.
【０００５】本発明において、前処理方法としては、オ
ゾン処理法および過酸化水素あるいは塩素を添加して紫
外線を照射する方法を行うことができる。オゾン処理に
は通常のオゾン発生装置を用いることができ、その発生
量は、廃水量２００ｍｌ〜５リットルに対して（有害物
質０．１〜３ｇに対して）、０．５〜２．０ｇ／時間が
適当である。オゾン量が少ないと分解が不十分であり、
多すぎても効果は大きくならない。その際に、廃水をか
くはんすると通気量と通気時間を短縮することができ
る。過酸化水素と紫外線照射の方法では、廃水中の被処
理の濃度により異なるが、有害物質０．１ｇ当り３００
〜３０，０００ｐｐｍの過酸化水素を廃水に添加するの
が適当で、この廃水を直接あるいは石英ガラスを通し
て、紫外線ランプで、照射する。塩素を添加して紫外線
照射する場合は、塩素の量は有害物質１ｇ当り２ｇ以上
が好ましく、この量が少なすぎると効果が小さく、多す
ぎると後処理が必要である。紫外線照射は、２００〜４
００ｎｍの光を被処理物質の濃度により異なるが、３０
分間以上照射するのが好ましい。本発明において、有害
物質とは廃水中の汚染物質をいい、人体に有害であるか
どうかではなく、環境保全上有害除去されることが必要
な物質をいう。In the present invention, as a pretreatment method, an ozone treatment method and a method of irradiating with ultraviolet rays by adding hydrogen peroxide or chlorine can be carried out. A normal ozone generator can be used for the ozone treatment, and the generated amount thereof is 0.5 to 2.0 g / for wastewater amount of 200 ml to 5 liters (for harmful substances of 0.1 to 3 g). Time is appropriate. If the amount of ozone is small, the decomposition is insufficient,
If too much, the effect does not increase. At that time, agitating the waste water can reduce the aeration amount and the aeration time. With the method of hydrogen peroxide and UV irradiation, it depends on the concentration of the treated substance in the wastewater, but it is 300 per 0.1g of harmful substances.
It is suitable to add hydrogen peroxide of about 30,000 ppm to the waste water, and the waste water is irradiated with an ultraviolet lamp directly or through quartz glass. When adding chlorine and irradiating with ultraviolet rays, the amount of chlorine is preferably 2 g or more per 1 g of harmful substances. If the amount is too small, the effect is small, and if it is too large, post-treatment is required. UV irradiation is 200-4
The light of 00 nm varies depending on the concentration of the substance to be treated,
It is preferable to irradiate for more than one minute. In the present invention, the toxic substance refers to a pollutant in wastewater, and refers to a substance that needs to be removed toxicly for environmental protection, not whether it is harmful to the human body.
【０００６】次いでこの前処理した廃水に半導体粉末を
懸濁する、あるいは半導体粉末を固定化した膜と廃水を
接触させる。この廃水に直接あるいはガラス容器を通し
て光照射を行う。半導体としては種々の金属酸化物を用
いることができるが、二酸化チタン（ルチルおよびアナ
タース）、酸化亜鉛、三酸化タングステンが好ましい。
半導体粉末の濃度は、廃水中の有害物質１ｇに対し、
０．５〜１０ｇの範囲である。粉末の場合の粒度は０．
１〜３．０μｍである。光源には、出射光が紫外光およ
び可視光の一部を含んでいるランプを用いることができ
る。例えば高圧および低圧の水銀灯、キセノンランプお
よびハロゲンランプであり、さらに半導体が二酸化チタ
ン、三酸化タングステンの場合には、太陽光を用いるこ
ともできる。Then, the semiconductor powder is suspended in the pretreated waste water, or the waste water is brought into contact with the membrane on which the semiconductor powder is immobilized. The wastewater is irradiated with light directly or through a glass container. Although various metal oxides can be used as the semiconductor, titanium dioxide (rutile and anatase), zinc oxide, and tungsten trioxide are preferable.
The concentration of semiconductor powder is 1 g of harmful substances in wastewater,
It is in the range of 0.5 to 10 g. In the case of powder, the particle size is 0.
It is 1 to 3.0 μm. A lamp whose emitted light contains part of ultraviolet light and visible light can be used as the light source. For example, high and low pressure mercury lamps, xenon lamps and halogen lamps, and when the semiconductor is titanium dioxide or tungsten trioxide, sunlight can also be used.
【０００７】[0007]
【発明の効果】廃水中の有害物質が短時間に完全分解し
て、無害な無機物質に変換される。INDUSTRIAL APPLICABILITY Hazardous substances in wastewater are completely decomposed in a short time and converted into harmless inorganic substances.
【０００８】[0008]
【実施例】以下に本発明を実施例に基づきさらに詳細に
説明する。EXAMPLES The present invention will be described in more detail based on the following examples.
【０００９】実施例１ 市販の農薬スミチオン（商品名、有機リン酸エステル系
化合物）を１５４ｐｐｍ（全有機炭素量６０ｐｐｍ）含
む廃水２５０ｍｌにオゾンを２．０ｇ／時間の速度で３
時間通気した。このときの廃水中の全有機炭素量を測定
すると５２ｐｐｍであった。これの２５ｍｌを取り、こ
れに７５ｍｇの二酸化チタン（粒径１．３μｍ）を加え
てかくはんして懸濁させた。この懸濁液を５００Ｗの高
圧水銀灯により照射した。１時間後に全有機炭素量が３
８ｐｐｍ、また４時間後には６ｐｐｍに減少した。オゾ
ン酸化処理を行なわずに光触媒処理のみを行うと、６時
間後に全有機炭素量が５１ｐｐｍに減少したに過ぎなか
った。また後段の二酸化チタンを加えての処理を行わず
に、前段のオゾンの通気を７時間行ったが、全有機炭素
量は５０ｐｐｍに減少したにすぎなかった。Example 1 250 ml of waste water containing 154 ppm of commercial pesticide Sumithion (trade name, organophosphate compound) (total organic carbon amount 60 ppm) was supplemented with ozone at a rate of 2.0 g / hour.
Aerated for hours. The total organic carbon content in the wastewater at this time was 52 ppm. 25 ml of this was taken, and 75 mg of titanium dioxide (particle size: 1.3 μm) was added thereto, and the mixture was stirred and suspended. The suspension was irradiated with a 500 W high pressure mercury lamp. Total organic carbon content is 3 after 1 hour
It decreased to 8 ppm and 6 ppm after 4 hours. When only the photocatalytic treatment was performed without performing the ozone oxidation treatment, the total amount of organic carbon was only reduced to 51 ppm after 6 hours. Further, ozone was aerated for 7 hours without performing the treatment of adding titanium dioxide in the latter stage, but the total amount of organic carbon was only reduced to 50 ppm.
【００１０】実施例２ 市販の農薬ＤＥＰを１６３ｐｐｍ（全有機炭素量４０ｐ
ｐｍ）含む廃水に、実施例１と同様にしてオゾンを通気
した。２時間、４時間および６時間後の全有機炭素量は
それぞれ３８、３７、３８ｐｐｍであった。これを実施
例１と同様にして、二酸化チタンにより光触媒処理を行
なうと、オゾン２時間通気の廃水では３時間後に９ｐｐ
ｍとなり、４時間通気の廃水では２時間後に１０ｐｐｍ
となった。一方オゾン前処理を行わないと、６時間で３
６ｐｐｍに減少したのみであった。Example 2 163 ppm of commercially available pesticide DEP (total organic carbon amount 40 p
The waste water containing pm) was aerated with ozone in the same manner as in Example 1. The total organic carbon contents after 2 hours, 4 hours, and 6 hours were 38, 37, and 38 ppm, respectively. When this was subjected to a photocatalytic treatment with titanium dioxide in the same manner as in Example 1, it was 9 pp after 3 hours in wastewater aerated with ozone for 2 hours.
m and becomes 10 ppm after 2 hours in the wastewater aerated for 4 hours.
Became. On the other hand, if ozone pretreatment is not performed, it takes 3 hours in 6 hours.
It was only reduced to 6 ppm.
【００１１】実施例３ 農薬のスミチオンを２１ｐｐｍ（全有機炭素量８．２ｐ
ｐｍ）含む廃水に、実施例１と同様にしてオゾンを通気
した。４時間までに全有機炭素量は殆ど減少しなかっ
た。１時間通気の廃水に実施例１と同様にして二酸化チ
タンを加えて光触媒処理を行った。２時間で全有機炭素
量が０となった。また２時間通気した廃水では１時間３
０分の光触媒処理で全有機炭素量が０になった。Example 3 21 ppm of pesticide Sumithion (total organic carbon amount 8.2 p
The waste water containing pm) was aerated with ozone in the same manner as in Example 1. By 4 hours, the total amount of organic carbon was hardly reduced. Titanium dioxide was added to the waste water aerated for 1 hour in the same manner as in Example 1 to perform photocatalytic treatment. The total amount of organic carbon became 0 in 2 hours. For wastewater that has been aerated for 2 hours, 1 hour 3
The total amount of organic carbon became 0 by the photocatalytic treatment for 0 minutes.
【００１２】実施例４ 農薬のアシュラムを５７５ｐｐｍ（全有機炭素量２４０
ｐｐｍ）含む廃水に、実施例１と同様にしてオゾン通気
を行なった。２時間後に全有機炭素量が１６５ｐｐｍと
なり、以後６時間までほとんど減少しなかった。４時間
オゾン通気後の廃水に、実施例１と同様にして二酸化チ
タンを加えて光触媒処理を行った。５時間後に全有機炭
素量が３０ｐｐｍに減少した。また６時間オゾン通気廃
水では５時間の光触媒処理で１０ｐｐｍとなった。Example 4 The pesticide ashram was added at 575 ppm (total organic carbon amount: 240
The waste water containing (ppm) was aerated with ozone in the same manner as in Example 1. After 2 hours, the total amount of organic carbon reached 165 ppm, and it was hardly reduced until 6 hours thereafter. Titanium dioxide was added to the waste water after ozone aeration for 4 hours in the same manner as in Example 1 to perform photocatalytic treatment. After 5 hours, the total amount of organic carbon was reduced to 30 ppm. Also, in the case of ozone aeration wastewater for 6 hours, it became 10 ppm after 5 hours of photocatalytic treatment.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０２Ｆ 1/72 １０１ 9045−4Ｄ 1/76 Ａ 9045−4Ｄ 1/78 9045−4Ｄ 9/00 Ｚ 7446−4Ｄ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical display location C02F 1/72 101 9045-4D 1/76 A 9045-4D 1/78 9045-4D 9/00 Z 7446-4D
Claims (4)
存在下で光照射して有害物質を分解処理することを特徴
とする廃水処理方法。1. A method of treating wastewater, which comprises oxidizing the wastewater and then irradiating it in the presence of a semiconductor catalyst to decompose harmful substances.
た膜、もしくは半導体薄膜として用いられることを特徴
とする請求項１記載の廃水処理方法。2. The wastewater treatment method according to claim 1, wherein the catalyst is used as a semiconductor powder, a film having the powder immobilized thereon, or a semiconductor thin film.
化タングステンから選ばれたことを特徴とする請求項１
記載の廃水処理方法。3. The catalyst is selected from titanium dioxide, zinc oxide and tungsten trioxide.
The described wastewater treatment method.
下での過酸化水素処理又は紫外線照射下での塩素処理の
いずれかを行うことを特徴とする請求項１記載の廃水処
理方法。4. The wastewater treatment method according to claim 1, wherein as the oxidation treatment, either ozone aeration, hydrogen peroxide treatment under ultraviolet irradiation, or chlorine treatment under ultraviolet irradiation is performed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4173863A JPH0736912B2 (en) | 1992-06-08 | 1992-06-08 | Photocatalytic wastewater treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4173863A JPH0736912B2 (en) | 1992-06-08 | 1992-06-08 | Photocatalytic wastewater treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05337469A true JPH05337469A (en) | 1993-12-21 |
| JPH0736912B2 JPH0736912B2 (en) | 1995-04-26 |
Family
ID=15968538
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4173863A Expired - Lifetime JPH0736912B2 (en) | 1992-06-08 | 1992-06-08 | Photocatalytic wastewater treatment method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0736912B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000078680A1 (en) * | 1999-06-21 | 2000-12-28 | Mitsui Engineering & Shipbuilding Co., Ltd. | Method and apparatus for purifying water |
| WO2008113128A1 (en) * | 2007-03-19 | 2008-09-25 | Viva Blu Pty Ltd | Method and apparatus for effecting a predetermined transformation |
| JP2014230603A (en) * | 2013-05-28 | 2014-12-11 | 三菱重工業株式会社 | Decomposition apparatus of tributyl phosphate (tbp) in waste oil or waste liquid |
-
1992
- 1992-06-08 JP JP4173863A patent/JPH0736912B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000078680A1 (en) * | 1999-06-21 | 2000-12-28 | Mitsui Engineering & Shipbuilding Co., Ltd. | Method and apparatus for purifying water |
| WO2008113128A1 (en) * | 2007-03-19 | 2008-09-25 | Viva Blu Pty Ltd | Method and apparatus for effecting a predetermined transformation |
| JP2014230603A (en) * | 2013-05-28 | 2014-12-11 | 三菱重工業株式会社 | Decomposition apparatus of tributyl phosphate (tbp) in waste oil or waste liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0736912B2 (en) | 1995-04-26 |
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