JP2640420B2 - Photo-oxidation treatment method - Google Patents
Photo-oxidation treatment methodInfo
- Publication number
- JP2640420B2 JP2640420B2 JP5346926A JP34692693A JP2640420B2 JP 2640420 B2 JP2640420 B2 JP 2640420B2 JP 5346926 A JP5346926 A JP 5346926A JP 34692693 A JP34692693 A JP 34692693A JP 2640420 B2 JP2640420 B2 JP 2640420B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- fine particles
- photo
- oxidation treatment
- catalyst fine
- 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 - Fee Related
Links
- 238000000034 method Methods 0.000 title claims description 22
- 238000007539 photo-oxidation reaction Methods 0.000 title claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 239000003054 catalyst Substances 0.000 claims description 39
- 239000010419 fine particle Substances 0.000 claims description 36
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 11
- 239000004408 titanium dioxide Substances 0.000 claims description 10
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 description 16
- 239000012528 membrane Substances 0.000 description 9
- 238000000108 ultra-filtration Methods 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Catalysts (AREA)
Description
【０００１】[0001]
【産業上の利用分野】この発明は、光酸化処理法に使用
した二酸化チタン等の触媒微粒子の洗浄・再生方法に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for cleaning and regenerating fine catalyst particles such as titanium dioxide used in a photo-oxidation treatment method.
【０００２】[0002]
【従来の技術】従来、テトロクロロエチレンなどのハロ
ゲン化有機物を含む排水、塩素剤と有機物質との反応に
よって生成される発ガン性物質は、液体の状態で分解し
て無害化する方法がなく、このためこれまで高温で燃焼
させて分解するとか、コンクリート中に詰めて廃棄する
などの方法が採用されていたが、何れの方法も二次公害
の発生の問題がある。2. Description of the Related Art Conventionally, there is no method for decomposing effluents containing halogenated organic substances such as tetrochloroethylene and carcinogenic substances produced by the reaction between chlorinating agents and organic substances in a liquid state. For this reason, methods such as burning at a high temperature to decompose or packing in concrete and discarding have been adopted, but all of these methods have a problem of secondary pollution.
【０００３】これに対して、被処理水中に二酸化チタン
等の触媒微粒子を懸濁させた被処理水中に紫外線を照射
させて行う光酸化処理法は、これら従来の廃水処理技術
では処理できなかったテトラクロロエチレン等のハロゲ
ン化有機物を含む廃水中の有機物を分解できるので、二
次公害を防止する面から注目されている。On the other hand, the photo-oxidation treatment method of irradiating the treated water in which the catalyst fine particles such as titanium dioxide are suspended in the treated water with ultraviolet rays cannot be treated by the conventional wastewater treatment techniques. Since it can decompose organic substances in wastewater containing halogenated organic substances such as tetrachloroethylene, it is attracting attention from the viewpoint of preventing secondary pollution.
【０００４】[0004]
【発明が解決しようとする問題点】しかし、この方法に
おいては使用後の酸化チタン等の触媒微粒子を処理後の
水中から分離、回収が極めて困難であるという問題点が
あり、また使用後の触媒微粒子の再利用の問題点があ
る。However, this method has a problem that it is extremely difficult to separate and recover used catalyst fine particles such as titanium oxide from the treated water, and also to use the used catalyst. There is a problem of reusing fine particles.
【０００５】前者の問題については、本願発明者は先に
二酸化チタンを含む処理水を限外濾過膜を通過させて二
酸化チタン微粒子を処理水を分離して回収する方法を提
案した( 特願平1-118581号）。Regarding the former problem, the inventor of the present application has previously proposed a method of separating treated water containing titanium dioxide by passing it through an ultrafiltration membrane to separate and collect the treated water (Japanese Patent Application No. Hei. 1-118581).
【０００６】しかし、この方法では限外濾過膜で捕集し
た触媒微粒子を処理槽に戻して何度でも使用できるが、
触媒微粒子を被処理水中で繰り返し使用するうちに、触
媒微粒子の表面に有機物或は無機物等が錯体化して固着
し、或は触媒微粒子の表面が着色され、このため徐々に
触媒としての機能が低下することになる。However, in this method, the catalyst fine particles collected by the ultrafiltration membrane can be returned to the treatment tank and used repeatedly.
As the catalyst fine particles are repeatedly used in the water to be treated, organic or inorganic substances are complexed and fixed on the surface of the catalyst fine particles, or the surface of the catalyst fine particles is colored, so that the function as a catalyst gradually decreases. Will do.
【０００７】しかも、これら触媒表面に付着した錯体等
は水洗等では容易に剥離ぜず、また一般のアルカリ剤、
酸性剤等を使用して溶解させる場合には、溶解後の廃液
の処理が不完全の場合には二次公害の問題を引き起こす
ことになる。Further, the complex and the like adhering to the surface of the catalyst are not easily separated by washing with water or the like, and are not easily removed by a general alkali agent,
When dissolving using an acidic agent or the like, if the treatment of the waste liquid after dissolution is incomplete, a problem of secondary pollution will be caused.
【０００８】そこで、二酸化チタン等の触媒微粒子をあ
る程度使用した後は、これを廃棄して新しい触媒に取り
替えることが行われていたが、これは光酸化処理法のコ
ストを引き上げる大きな要因となっており、この点から
後者の問題の完全な解決が要望されている。Therefore, after the catalyst fine particles such as titanium dioxide are used to some extent, they are discarded and replaced with a new catalyst, but this is a major factor in raising the cost of the photo-oxidation treatment method. Therefore, a complete solution to the latter problem is desired from this point.
【０００９】[0009]
【問題点を解決するための手段】以上の問題点を解決す
るため、この発明では被処理水中に触媒微粒子を懸濁さ
せ、紫外線を照射して被処理水の有機物分解乃至殺菌処
理をする光酸化処理工程と処理された水とこれに含まれ
る触媒微粒子を分離する分離工程からなり、分離工程で
分離された処理水を光酸化処理工程に戻して処理する光
酸化処理法において、分離工程で分離された触媒微粒子
を洗浄槽内の洗浄水中でオゾン乃至エアー曝気しながら
洗浄・再生し、再生された触媒微粒子を上記光酸化処理
工程に戻すようにした光酸化処理法を提案するものであ
る。Means for Solving the Problems In order to solve the above problems, in the present invention, catalyst fine particles are suspended in water to be treated and irradiated with ultraviolet light to decompose or sterilize organic substances in the water to be treated. The photo-oxidation method comprises an oxidation treatment step and a separation step of separating treated water and catalyst fine particles contained in the water, and the treated water separated in the separation step is returned to the photo-oxidation treatment step for treatment. The present invention proposes a photo-oxidation treatment method in which separated catalyst fine particles are washed and regenerated in a cleaning tank in a cleaning water while aerating with ozone or air, and the regenerated catalyst fine particles are returned to the photo-oxidation treatment step. .
【００１０】[0010]
【作用】即ち、この発明のように洗浄水中でオゾン乃至
エアー曝気しながら触媒微粒子を洗浄すると、触媒微粒
子の表面に付着した錯体等にオゾン乃至エアーの気泡が
入り込み、その酸化力と浮遊力でこれら付着物を触媒微
粒子の表面から剥離する。That is, when the catalyst fine particles are washed while aerating the ozone or air in the washing water as in the present invention, bubbles of the ozone or air enter into the complex or the like adhering to the surface of the catalyst fine particles, and their oxidizing power and buoyancy force. These deposits are separated from the surfaces of the catalyst fine particles.
【００１１】しかも、ここでエアー勿論のこと、オゾン
についても分解して酸素となるため、全く二次公害の問
題がない。In addition, since not only air but also ozone is decomposed into oxygen, there is no problem of secondary pollution.
【００１２】また、以上のようなオゾン乃至エアー曝気
による化学的物理的な洗浄方法に加えて、アルカリ水、
酸性水による触媒微粒子の表面の化学的な洗浄方法、超
音波振動による物理的な洗浄方法を行ってもよい。In addition to the above-mentioned chemical and physical cleaning method using ozone or air aeration, alkaline water,
A chemical cleaning method of the surface of the catalyst fine particles with acidic water or a physical cleaning method with ultrasonic vibration may be performed.
【００１３】なお、化学的な洗浄方法に使用するアルカ
リ水、酸性水としては例えば５％の食塩水の電気分解に
よって生成したアルカリ水と酸性水が二次公害防止の面
から好ましい。As alkaline water and acidic water used in the chemical cleaning method, for example, alkaline water and acidic water generated by electrolysis of 5% saline solution are preferable from the viewpoint of preventing secondary pollution.
【００１４】即ち、例えば５％食塩水の電気分解によっ
て、約pH12のアルカリ水と約pH2、ORP(酸化還元電位)100
0mV 以上の酸性水が得られるが、このうち酸性水には対
象物の電子を奪って酸化し、自身は中性化し、残留性が
ない、またアルカリ水には中性化する前の酸性水と混ぜ
ることにより、中性化して、何れも二次公害の問題を生
ずることがない。That is, for example, by electrolysis of a 5% saline solution, an alkaline water having a pH of about 12 and a pH of about 2, and an ORP (oxidation-reduction potential) of 100
Acidic water of 0 mV or more is obtained.Of these, acidic water deprives the target of electrons and oxidizes, neutralizes itself and has no persistence, and alkaline water has no acidity before neutralization. By mixing with any of them, they are neutralized and neither cause the problem of secondary pollution.
【００１５】[0015]
【実施例】以下、図示の実施例に基づいてこの発明を詳
細に説明すると、図１はこの発明の洗浄工程を示すもの
で、１は中端部に洗浄水抜きバルブ２、下端部に触媒微
粒子抜きバルブ３を有する洗浄槽であって、洗浄槽１内
には撹拌機４、水位電極５が挿入され、またその底部に
は散気板６を臨ませ、更に洗浄槽１の側壁には超音波振
動器７が取り付けられる。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the illustrated embodiment. FIG. 1 shows a cleaning process of the present invention, wherein 1 is a cleaning water drain valve 2 at a middle end, and a catalyst is a lower end. A washing tank having a particulate removal valve 3, a stirrer 4 and a water level electrode 5 are inserted into the washing tank 1, and a diffuser plate 6 faces the bottom thereof. The ultrasonic vibrator 7 is attached.
【００１６】洗浄槽１の下方には水抜き槽８を位置さ
せ、この水抜き槽８には内部にフィルター篭９が収納さ
れ、更にその側部には洗浄水抜きバルブ10が設けられて
いる。A drainage tank 8 is located below the washing tank 1, and a filter basket 9 is housed in the drainage tank 8 and a washing water draining valve 10 is provided on a side portion thereof. .
【００１７】光酸化処理工程11から送られた使用済みの
二酸化チタン等の触媒微粒子12を洗浄槽１内に供給され
るが、ここで図２に基づいて光酸化処理工程11を詳細に
説明すると、これに使用する光酸化処理装置は紫外線ラ
ンプ13を内蔵した処理槽14と限外濾過膜15を内蔵した分
離槽16とからなり、被処理水は触媒微粒子12と共に処理
槽14内に供給し、ここでヒータ17により加熱しながら紫
外線照射を受け、これにより二酸化チタン微粒子の触媒
作用により被処理水中の有機物の分解、殺菌処理等が行
われる。The used catalyst fine particles 12 such as titanium dioxide sent from the photo-oxidation treatment step 11 are supplied into the cleaning tank 1. Here, the photo-oxidation treatment step 11 will be described in detail with reference to FIG. The photo-oxidation treatment apparatus used for this comprises a treatment tank 14 having a built-in ultraviolet lamp 13 and a separation tank 16 having a built-in ultrafiltration membrane 15. Here, ultraviolet rays are received while being heated by the heater 17, whereby the decomposition of organic matter in the water to be treated and the sterilization treatment are performed by the catalytic action of the titanium dioxide fine particles.
【００１８】処理された水は、圧送ポンプ18により分離
槽16に送り、限外濾過膜15を通過させることにより、触
媒微粒子12は限外濾過膜15で捕集し、処理水と分離し、
限外濾過膜15で捕集された触媒微粒子12は洗浄水をポン
プ19により限外濾過膜15の内側に圧送することにより、
限外濾過膜15より解放し、解放された触媒微粒子12はそ
の一部は処理槽14に戻し、その一部は上述のように洗浄
槽１内に供給される。The treated water is sent to a separation tank 16 by a pressure pump 18 and passed through an ultrafiltration membrane 15, whereby the catalyst fine particles 12 are collected by the ultrafiltration membrane 15 and separated from the treated water.
The catalyst fine particles 12 collected by the ultrafiltration membrane 15 are pumped with washing water to the inside of the ultrafiltration membrane 15 by the pump 19,
A part of the released catalyst fine particles 12 released from the ultrafiltration membrane 15 is returned to the treatment tank 14, and a part thereof is supplied into the cleaning tank 1 as described above.
【００１９】また、洗浄槽１には純水或は水道水等の洗
浄水を供給し、この供給は水位電極５により洗浄槽１が
所定の水位に達した時に停止する。Further, cleaning water such as pure water or tap water is supplied to the cleaning tank 1, and the supply is stopped when the cleaning tank 1 reaches a predetermined water level by the water level electrode 5.
【００２０】使用済みの触媒微粒子12と洗浄水の収容さ
れた洗浄槽１では撹拌機４で内部を撹拌し、更に超音波
振動器７で振動させると共に、散気板６よりオゾン乃至
エアーを供給して触媒微粒子12の表面を曝気処理しなが
ら洗浄を行う。In the washing tank 1 containing the used catalyst fine particles 12 and washing water, the inside is stirred by the stirrer 4, further vibrated by the ultrasonic vibrator 7, and ozone or air is supplied from the diffuser plate 6. Then, the surface of the catalyst fine particles 12 is washed while being aerated.
【００２１】全ての洗浄の終了後、バルブ３を開き、洗
浄された触媒微粒子12を洗浄水と共に水抜き槽８に移
し、水抜き槽８では洗浄された触媒微粒子12はフィルタ
ー篭９に収納され、一方洗浄水はバルブ10を開くことに
より、排出され、洗浄された触媒微粒子12を処理槽14に
戻して再利用することができる。After completion of all washing, the valve 3 is opened, and the washed catalyst fine particles 12 are transferred together with the washing water to the drain tank 8, where the washed catalyst fine particles 12 are stored in the filter basket 9. On the other hand, the cleaning water is discharged by opening the valve 10, and the washed catalyst fine particles 12 can be returned to the processing tank 14 and reused.
【００２２】[0022]
【発明の効果】以上要するに、この発明によれば光酸化
処理法に使用した触媒微粒子表面の錯体等の付着物を二
次公害を起こすことなく、剥離除去することができる。In summary, according to the present invention, deposits such as complexes on the surface of catalyst fine particles used in the photo-oxidation treatment can be removed without causing secondary pollution.
【００２３】また、この発明によれば高価な二酸化チタ
ン等の触媒粒子を繰り返して再利用できるため、光酸化
処理法にコスト低減に大きな貢献をすることができる。Further, according to the present invention, since expensive catalyst particles such as titanium dioxide can be repeatedly reused, it is possible to greatly contribute to cost reduction in the photo-oxidation treatment method.
【図１】 この発明の光酸化処理工程で使用した触媒微
粒子の洗浄工程を示す図FIG. 1 is a diagram showing a washing step of catalyst fine particles used in a photo-oxidation treatment step of the present invention.
【図２】 触媒微粒子を使用する光酸化処理工程を示す
図FIG. 2 is a view showing a photo-oxidation treatment step using catalyst fine particles.
【符号の説明】 １は洗浄槽 ２は洗浄水抜きバルブ ３は触媒微粒子抜きバルブ ４は撹拌機 ５は水位電極 ６は散気板 ７は超音波振動器 ８は水抜き槽 ９はフィルター篭 10は洗浄水抜きバルブ 11は光酸化処理工程 12は二酸化チタン等の触媒微粒子 13は紫外線ランプ 14は処理槽 15は限外濾過膜 16は分離槽 17はヒータ 18は圧送ポンプ 19はポンプ[Description of Signs] 1 is a washing tank 2 is a washing water drain valve 3 is a catalyst fine particle removing valve 4 is a stirrer 5 is a water level electrode 6 is a diffuser plate 7 is an ultrasonic vibrator 8 is a water drain tank 9 is a filter basket 10 Is a cleaning water drain valve 11 is a photo-oxidation treatment process 12 is a catalyst fine particle such as titanium dioxide 13 is an ultraviolet lamp 14 is a treatment tank 15 is an ultrafiltration membrane 16 is a separation tank 17 is a heater 18 is a pressure pump 19 is a pump
Claims (1)
外線を照射して被処理水の有機物分解乃至殺菌処理をす
る光酸化処理工程と処理された水とこれに含まれる触媒
微粒子を分離する分離工程からなり、分離工程で分離さ
れた処理水を光酸化処理工程に戻して処理する光酸化処
理法において、触媒微粒子として二酸化チタン微粒子を
使用し、分離工程で分離された二酸化チタン微粒子を洗
浄槽内の洗浄水中でオゾン乃至エアー曝気しながら洗浄
・再生した後、上記光酸化処理工程に戻すようにしたこ
とを特徴とする光酸化処理法。1. A photo-oxidation treatment step in which catalyst fine particles are suspended in water to be treated and irradiated with ultraviolet rays to decompose or sterilize organic substances in the water to be treated, and the treated water is separated from the catalyst fine particles contained therein. In the photo-oxidation treatment method in which the treated water separated in the separation step is returned to the photo-oxidation treatment step for treatment, titanium dioxide fine particles are used as catalyst fine particles.
A photo-oxidation treatment , wherein the titanium dioxide fine particles separated in the separation step are washed and regenerated while aerating with ozone or air in washing water in a washing tank, and then returned to the photo-oxidation treatment step. Law.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5346926A JP2640420B2 (en) | 1993-12-27 | 1993-12-27 | Photo-oxidation treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5346926A JP2640420B2 (en) | 1993-12-27 | 1993-12-27 | Photo-oxidation treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07185340A JPH07185340A (en) | 1995-07-25 |
| JP2640420B2 true JP2640420B2 (en) | 1997-08-13 |
Family
ID=18386754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5346926A Expired - Fee Related JP2640420B2 (en) | 1993-12-27 | 1993-12-27 | Photo-oxidation treatment method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2640420B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL1001474C2 (en) * | 1995-10-23 | 1997-04-25 | Legerlede Holding B V I O | Purification of contaminated water |
| JP2000279975A (en) * | 1999-03-30 | 2000-10-10 | Kanagawa Acad Of Sci & Technol | Water treatment by using photo-catalyst and ozone in combination and its device |
| AU2004234223A1 (en) * | 2003-05-02 | 2004-11-11 | Japan Techno Co., Ltd. | Active antiseptic water or active antiseptic water system fluid, and method and device for production the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5494487A (en) * | 1978-01-10 | 1979-07-26 | Kobe Steel Ltd | Activation of catalyst |
| JPS6480444A (en) * | 1987-09-22 | 1989-03-27 | Mitsubishi Heavy Ind Ltd | Regeneration of denitration catalyst |
-
1993
- 1993-12-27 JP JP5346926A patent/JP2640420B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07185340A (en) | 1995-07-25 |
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