JP2001029942A - Photocatalytic decomposition method of pcb - Google Patents
Photocatalytic decomposition method of pcbInfo
- Publication number
- JP2001029942A JP2001029942A JP11208162A JP20816299A JP2001029942A JP 2001029942 A JP2001029942 A JP 2001029942A JP 11208162 A JP11208162 A JP 11208162A JP 20816299 A JP20816299 A JP 20816299A JP 2001029942 A JP2001029942 A JP 2001029942A
- Authority
- JP
- Japan
- Prior art keywords
- pcb
- reaction
- decomposition
- photocatalytic
- photocatalytic decomposition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 63
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 239000007788 liquid Substances 0.000 claims abstract description 30
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000013032 photocatalytic reaction Methods 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 39
- 239000003002 pH adjusting agent Substances 0.000 claims description 22
- 238000006303 photolysis reaction Methods 0.000 claims description 14
- 230000015843 photosynthesis, light reaction Effects 0.000 claims description 10
- XWNSFEAWWGGSKJ-UHFFFAOYSA-N 4-acetyl-4-methylheptanedinitrile Chemical compound N#CCCC(C)(C(=O)C)CCC#N XWNSFEAWWGGSKJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004153 Potassium bromate Substances 0.000 claims description 4
- 235000019396 potassium bromate Nutrition 0.000 claims description 4
- 229940094037 potassium bromate Drugs 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 5
- 239000000460 chlorine Substances 0.000 description 21
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 20
- 235000017168 chlorine Nutrition 0.000 description 17
- 229910052801 chlorine Inorganic materials 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 11
- 239000003921 oil Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 6
- 238000005215 recombination Methods 0.000 description 5
- 230000006798 recombination Effects 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 3
- 150000001804 chlorine Chemical class 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 238000006864 oxidative decomposition reaction Methods 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000004519 manufacturing process Methods 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
- 238000006552 photochemical reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102100033040 Carbonic anhydrase 12 Human genes 0.000 description 1
- 102100033041 Carbonic anhydrase 13 Human genes 0.000 description 1
- 102100033007 Carbonic anhydrase 14 Human genes 0.000 description 1
- 102100032566 Carbonic anhydrase-related protein 10 Human genes 0.000 description 1
- 101000867855 Homo sapiens Carbonic anhydrase 12 Proteins 0.000 description 1
- 101000867860 Homo sapiens Carbonic anhydrase 13 Proteins 0.000 description 1
- 101000867862 Homo sapiens Carbonic anhydrase 14 Proteins 0.000 description 1
- 101000867836 Homo sapiens Carbonic anhydrase-related protein 10 Proteins 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 101100219325 Phaseolus vulgaris BA13 gene Proteins 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、高塩素置換ＰＣＢ
を含む廃トランス油などのＰＣＢ含有液を安全に、かつ
簡単に光分解処理するＰＣＢの光触媒分解方法に関す
る。The present invention relates to a high chlorine-substituted PCB.
The present invention relates to a photocatalytic decomposition method of PCB for safely and easily photodecomposing a PCB-containing liquid, such as waste transformer oil, containing PCB.
【０００２】[0002]
【従来の技術】ＰＣＢは、ポリクロロビフェニルの略称
であり、ビフェニルの２個以上の水素を塩素で置換した
化合物で、塩素の数や置換位置により種々の化合物（理
論上２０９種類の異性体）が知られている。ＰＣＢは、
熱に対して安定で、電気絶縁性が高いという優れた特性
を有しているので、かつてトランス油、コンデンサー等
の電気機器関係、熱媒体、ノンカーボン紙などに用いら
れていた。一般に、トランス油等で使用されているＰＣ
Ｂは、これら単体の混合物であり、通常１００以上の異
性体が含まれている。2. Description of the Related Art PCB is an abbreviation of polychlorobiphenyl, a compound in which two or more hydrogen atoms of biphenyl are substituted with chlorine, and various compounds (209 kinds of isomers in theory) depending on the number and substitution positions of chlorine. It has been known. PCB is
Because of its excellent properties of being stable to heat and having high electrical insulation properties, it was once used in transformer oils, electrical equipment such as condensers, heating media, non-carbon paper, and the like. Generally used for transformer oil etc.
B is a mixture of these simple substances, and usually contains 100 or more isomers.
【０００３】これらのＰＣＢは、極めて高い毒性を有
し、且つ難分解性物質（塩素数が多いほど更に難分解
性）であることから、第一種特定化学物質として、製
造、使用、輸入が禁止された後も、適切な処理方法が確
立されていなかった。そのため、１９７２年製造禁止よ
り以前に製造されたＰＣＢは、事業者により厳重に保管
されてきたが、近年、保管設備の老朽化等により、これ
らの漏えいによる、環境汚染の危険性が生じており、早
急な処理方法の確立が必要となっている。平成１０年に
なって、国のＰＣＢ処理基準が制定されたことを受け、
現在までに、幾つかのＰＣＢ分解技術が開発、実用化さ
れているが、これらの方法は、高温又は高圧な系による
分解反応であり、実用化には、それを制御するための複
雑、且つ巨大な設備が必要とする課題がある。[0003] Since these PCBs have extremely high toxicity and are hardly decomposable substances (the more the number of chlorines, the more difficult they are to decompose), their production, use, and import are specified as Class I specified chemical substances. Even after the ban, proper treatment methods had not been established. For this reason, PCBs manufactured before the production ban in 1972 have been strictly stored by businesses, but in recent years, due to aging storage facilities, there has been a risk of environmental pollution due to these leaks. Therefore, it is necessary to quickly establish a treatment method. In 1998, following the establishment of national PCB processing standards,
To date, several PCB decomposition technologies have been developed and put into practical use. However, these methods are decomposition reactions using a high-temperature or high-pressure system, and the practical use requires complicated and complicated methods for controlling them. There are issues that require huge equipment.
【０００４】一方、酸化チタンを用いた光化学分解反応
は、温度や圧力をかけることなく光エネルギーを化学的
エネルギーに変換し、有機物を分解できることが知られ
ている。しかしながら、この方法では、反応の進行と共
に、分解物質等の蓄積による酸化チタンの光化学活性
消失及び反応の停止、正孔と荷電子の再結合による反
応阻害が起こるため、トランス油等のような有機物中の
高塩素置換ＰＣＢ等の分解は不可能であった。[0004] On the other hand, it is known that a photochemical decomposition reaction using titanium oxide can convert light energy into chemical energy without applying temperature or pressure to decompose organic substances. However, in this method, with the progress of the reaction, the photochemical activity of titanium oxide is lost due to the accumulation of decomposed substances and the reaction is stopped, and the reaction is inhibited by the recombination of holes and valence electrons. Decomposition of the high chlorine-substituted PCB and the like in the interior was not possible.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、上記従来技
術の課題等に鑑み、これを解消しようとするものであ
り、高塩素置換ＰＣＢを含む廃トランス油などのＰＣＢ
含有液を安全に、かつ簡単に光分解処理するＰＣＢの光
触媒分解方法を提供することを目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems in the prior art, and has been made in order to solve the problem.
An object of the present invention is to provide a photocatalytic decomposition method for PCBs, which can safely and easily photodecompose a contained liquid.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記従来
技術の課題等について、鋭意検討した結果、酸化チタン
を用いたＰＣＢの光触媒分解方法において、特定の処理
剤等を用いることにより、上記目的のＰＣＢの光触媒分
解方法が得られることを見い出し、本発明を完成するに
至ったのである。すなわち、本発明は、次の(1)〜(5)に
存する。 (1) 酸化チタンを用いたＰＣＢの光触媒分解方法であっ
て、被処理液となるＰＣＢ含有液を反応制御剤により調
整し、この調整したＰＣＢ含有液を紫外線の照射下で光
触媒反応によりＰＣＢを光分解処理することを特徴とす
るＰＣＢの光触媒分解方法。 (2) 反応制御剤がｐＨ調製剤からなり、該ｐＨ調製剤に
より、ＰＣＢ含有液をｐＨ７．０〜８．０に調整しなが
ら光分解処理する上記(1)記載のＰＣＢの光触媒分解方
法。 (3) 反応制御剤が電子受溶体付与剤からなる上記(1)記
載のＰＣＢの光触媒分解方法。 (4) 電子受溶体付与剤が臭素酸カリウムからなる上記
(3)記載のＰＣＢの光触媒分解方法。 (5) 反応制御剤として、ｐＨ調製剤と電子受溶体付与剤
とを併用し、該ｐＨ調製剤により、ＰＣＢ含有液をｐＨ
７．０〜８．０に調整しながら光分解処理する上記(1)
又は(4)記載のＰＣＢの光触媒分解方法。 なお、本発明において「処理対象となるＰＣＢ」は、置
換塩素数の異なる全てのＰＣＢ異性体を処理対象とする
ことができ、例えば、高塩素置換ＰＣＢを含む廃トラン
ス油などのＰＣＢ含有液などが挙げられ、後述するよう
に分解効率の低い高塩素置換ＰＣＢまでも高効率で分解
処理することができるものである。Means for Solving the Problems The present inventors have conducted intensive studies on the above-mentioned problems of the prior art and the like. As a result, in a photocatalytic decomposition method of PCB using titanium oxide, by using a specific treating agent or the like, The inventors have found that a photocatalytic decomposition method of PCB having the above object can be obtained, and have completed the present invention. That is, the present invention resides in the following (1) to (5). (1) A method for photocatalytic decomposition of PCB using titanium oxide, in which a PCB-containing liquid to be treated is adjusted by a reaction control agent, and the adjusted PCB-containing liquid is subjected to a photocatalytic reaction under irradiation of ultraviolet rays. A photocatalytic decomposition method of PCB, which is subjected to a photolysis treatment. (2) The method for photocatalytic decomposition of PCB according to the above (1), wherein the reaction control agent comprises a pH adjuster, and the pH adjuster adjusts the pH of the PCB-containing solution to a pH of 7.0 to 8.0 by photolysis. (3) The method for photocatalytic decomposition of PCB according to the above (1), wherein the reaction control agent comprises an electron receiving material imparting agent. (4) The above wherein the electron acceptor-imparting agent comprises potassium bromate.
(3) The method for photocatalytic decomposition of PCB according to (3). (5) As a reaction control agent, a pH adjuster and an electron acceptor-imparting agent are used in combination, and the pH adjuster causes the PCB-containing solution to have a pH.
The above (1) in which the photolysis treatment is performed while adjusting to 7.0 to 8.0.
Or the photocatalytic decomposition method of PCB according to (4). In the present invention, the “PCB to be treated” can treat all PCB isomers having different substituted chlorine numbers, for example, a PCB-containing liquid such as waste transformer oil containing high chlorine-substituted PCB. As described later, even a high chlorine-substituted PCB having a low decomposition efficiency can be decomposed with high efficiency.
【０００７】[0007]
【発明の実施の形態】以下に、本発明の実施の形態を図
面を参照しながら詳しく説明する。本発明のＰＣＢの光
触媒分解方法は、酸化チタンを用いたＰＣＢの光触媒分
解方法であって、被処理液となるＰＣＢ含有液を反応制
御剤により調整し、この調整したＰＣＢ含有液を紫外線
の照射下で光触媒反応によりＰＣＢを光分解処理するこ
とを特徴とするものである。Embodiments of the present invention will be described below in detail with reference to the drawings. The photocatalytic decomposition method of PCB of the present invention is a photocatalytic decomposition method of PCB using titanium oxide, in which a PCB-containing liquid to be treated is adjusted with a reaction control agent, and the adjusted PCB-containing liquid is irradiated with ultraviolet rays. It is characterized in that the PCB is subjected to a photolysis treatment by a photocatalytic reaction below.
【０００８】本発明のＰＣＢの光触媒分解反応の機構を
図１により具体的に説明する。分解反応機構は、図１に
示されるように、ＴｉＯ2に紫外光（波長＜３９０ｎ
ｍ）が照射されると下記反応式（ｉ）に示すように、電
子励起による電荷分離（ｈ+とｅ-）が起こる。 ＴｉＯ2 ＋ ｈν → ｅ- ＋ ｈ+ ……（ｉ） ここで、上記正孔（ｈ+）は、ＯＨ-イオンと反応し、下
記反応式（ii）に示すように、・ＯＨ（ＯＨラジカル）
となる。なお、下記反応式（ii）において、ＯＨ-が消
費されるため、Ｈ+が増加し、ｐＨが低下する（本発明
ではｐＨ調整剤によりｐＨの低下を防止して反応の阻害
原因を除去する）。 ｈ+ ＋ ＯＨ- → ・ＯＨ ……（ii） また、上記反応式（ii）に生成した・ＯＨは、下記反応
式（iii）に示すように、ＰＣＢと酸化分解反応が行わ
れ、ＰＣＢが効率的に光分解処理されることとなる。 ・ＯＨ ＋ ＰＣＢ →ＣＯ2，ＨＣｌ，Ｈ2０ ……（iii） なお、本発明の光触媒分解反応において、上記反応式
（ｉ）で生成した電子（ｅ-）が、正孔（ｈ+）と再結合
してしまう場合もある。この場合、下記式に示すよう
に、熱を発生して消滅してしまう（反応が阻害され
る）。 ｅ- ＋ ｈ+ → △Ｈ（熱） これを防止するために電子受容体付与剤（ＫＢｒＯ3な
ど）を添加することにより再結合を防止することができ
る。 ｅ- ＋ ＫＢｒＯ3 → ・ＫＢｒＯ3 - ・ＫＢｒＯ3 - ＋ Ｈ+ → ・ＨＯ3 ＋ ＫＢｒ ・ＨＯ3 →・ＯＨ ＋ Ｏ２ The mechanism of the photocatalytic decomposition reaction of PCB of the present invention will be specifically described with reference to FIG. Decomposition reaction mechanism, as shown in FIG. 1, ultraviolet light TiO 2 (wavelength <390 N
When m) is irradiated, as shown in the following reaction formula (i), charge separation (h + and e − ) occurs by electronic excitation. TiO 2 + hν → e − + h + (i) Here, the above holes (h + ) react with OH − ions, and as shown in the following reaction formula (ii), .OH (OH radical )
Becomes In the following reaction formula (ii), OH − is consumed, so that H + increases and the pH decreases. (In the present invention, the pH is prevented from lowering by a pH adjuster to eliminate the cause of the reaction inhibition. ). h + + OH - → · OH ...... (ii) In addition, · OH produced in the above reaction formula (ii), as shown in the following reaction formula (iii), PCB and oxidative decomposition reaction takes place, PCB is Photolysis treatment is performed efficiently. OH + PCB → CO 2 , HCl, H 20 (iii) In the photocatalytic decomposition reaction of the present invention, the electrons (e − ) generated by the above reaction formula (i) are converted into holes (h + ). May be recombined. In this case, as shown in the following formula, heat is generated and disappears (reaction is inhibited). e − + h + → ΔH (heat) Recombination can be prevented by adding an electron acceptor-imparting agent (KBrO 3 or the like) to prevent this. e - + KBrO 3 → · KBrO 3 - · KBrO 3 - + H + → · HO 3 + KBr · HO 3 → · OH + O 2
【０００９】図２は、本発明の光触媒分解方法に用いる
装置の一例を示す図面である。この光触媒分解装置１０
は、反応槽１１内にランプ保護管１２で保護された波長
＜３８８ｎｍの紫外線を照射する紫外線ランプ１３が設
けられている。また、処理槽１１内に収容されるＰＣＢ
含有液は、ポンプ１４により循環される。なお、処理槽
１１内には更に必要に応じて撹拌装置を設けてもよい。
また、図示符号１５は反応制御剤を投入する投入口であ
る。FIG. 2 is a drawing showing an example of an apparatus used in the photocatalytic decomposition method of the present invention. This photocatalytic decomposition device 10
Is provided with an ultraviolet lamp 13 for irradiating ultraviolet rays having a wavelength <388 nm protected by a lamp protection tube 12 in a reaction tank 11. Also, the PCB accommodated in the processing tank 11
The liquid content is circulated by the pump 14. In addition, a stirring device may be further provided in the processing tank 11 as needed.
Reference numeral 15 denotes an inlet for charging the reaction control agent.
【００１０】本発明で処理するＰＣＢ含有液としては、
例えば、高塩素置換ＰＣＢを含む廃トランス油、または
ＰＣＢ廃液などが挙げられ、これらは、更に、有機溶剤
等の溶媒で溶解したものであってもよい。また、本発明
で用いる酸化チタンとしては、特に限定されるものでは
なく、例えば、市販のアナターゼ型が用いられ、これら
は、処理槽１１内に粉末または適宜な媒体表面に付着さ
せた状態で収容される。The PCB-containing liquid to be treated in the present invention includes:
For example, waste transformer oil containing high chlorine-substituted PCB, PCB waste liquid, and the like may be mentioned. These may be further dissolved in a solvent such as an organic solvent. The titanium oxide used in the present invention is not particularly limited. For example, commercially available anatase type is used, and these are stored in the processing tank 11 in a state of being attached to a powder or an appropriate medium surface. Is done.
【００１１】本発明では、酸化チタンによる光触媒分解
反応において、反応制御剤により反応活性を制御し、Ｐ
ＣＢの高効率分解処理を可能とするものである。本発明
で用いる反応制御剤としては、例えば、ｐＨ調製剤、電
子受溶体付与剤が挙げられる。ｐＨ調製剤は、ＴｉＯ２
による光化学反応では、上述の如く、ＯＨ-イオンが反
応により消費されるため、反応液のｐＨが、時間と共に
酸性側へ移行するので、反応液のｐＨを初期状態、すな
わち、ｐＨを７．０〜８．０に維持することを目的とし
て添加するものである。従って、添加量は上記ｐＨ範囲
内となるように添加される。ｐＨ調製剤としては、アル
カリ剤であれば特に限定されるものではなく、例えば、
ＮａＯＨ、ＫＯＨなどが挙げられる。このｐＨ調整によ
り、ＯＨ-イオンの供給、酸化分解生成物の酸性域
における反応阻害の防止により反応効率が改善されるこ
ととなる。処理槽で処理するＰＣＢ含有液のｐＨを上記
７．０〜８．０の範囲内で行うことにより、光触媒分解
反応が効率的に行われ、ＰＣＢが効率よく光分解処理さ
れることとなる。なお、光触媒分解装置１０の処理槽１
１に反応液のｐＨ自動測定装置を取り付け、ｐＨを７．
０〜８．０に維持するように、ｐＨ調製剤を投入口から
自動的に添加できる構成にすれば、自動化できる。In the present invention, in the photocatalytic decomposition reaction by titanium oxide, the reaction activity is controlled by a reaction control agent,
This enables highly efficient decomposition of CB. Examples of the reaction control agent used in the present invention include a pH adjuster and an electron acceptor-imparting agent. The pH adjusting agent is TiO 2
In the photochemical reaction according to the above, as described above, since the OH - ions are consumed by the reaction, the pH of the reaction solution shifts to the acidic side with the lapse of time. It is added for the purpose of maintaining at ~ 8.0. Therefore, the amount added is within the above-mentioned pH range. The pH adjuster is not particularly limited as long as it is an alkaline agent.
NaOH, KOH and the like. By this pH adjustment, the reaction efficiency is improved by supplying OH - ions and preventing the oxidative decomposition products from inhibiting the reaction in the acidic region. By performing the pH of the PCB-containing liquid to be treated in the treatment tank within the range of 7.0 to 8.0, the photocatalytic decomposition reaction is efficiently performed, and the PCB is efficiently subjected to the photolytic treatment. The processing tank 1 of the photocatalytic decomposition device 10
Attach an automatic pH measuring device for the reaction solution to 1 and adjust the pH to 7.
If the configuration is such that the pH adjusting agent can be automatically added from the inlet so as to maintain the pH at 0 to 8.0, the system can be automated.
【００１２】また、本発明で用いる電子受溶体付与剤
は、ＴｉＯ2による光化学反応では、上述の如く、反応
式（ｉ）で生成した電子（ｅ-）が、正孔（ｈ+）と再結
合し、熱を発生して消滅し、反応が阻害されることを防
止して、効率的に光触媒分解反応を行うために添加する
ものである。電子受溶体付与剤としては、電子（ｅ-）
と正孔（ｈ+）との再結合を防止できる電子受溶体とな
る剤であれば、特に限定されるものではなく、例えば、
臭素酸カリウム（ＫＢｒＯ3）、過酸化水素（Ｈ2Ｏ2）
などを挙げることができ、好ましくは、臭素酸カリウム
（ＫＢｒＯ3）である。電子受溶体付与剤の添加量は、
ＰＣＢ種、ＰＣＢ含有液量（濃度）などにより異なる
が、ＰＣＢ含有液（ＰＣＢ濃度１０ｍｇ／ｌ）全量に対
して、１０ｍｍｏｌ／ｌ（１７０ｍｇ／ｌ）程度であ
る。本発明では、反応制御剤として、ｐＨ調製剤と電子
受溶体付与剤とを併用し、ＰＣＢ含有液をｐＨ７．０〜
８．０に調整して光分解処理すれば、更に効率的にＰＣ
Ｂを効率よく光分解処理することができる。Further, the electron acceptor-imparting agent used in the present invention is such that, in the photochemical reaction with TiO 2 , as described above, the electron (e − ) generated by the reaction formula (i) is converted into a hole (h + ). It is added for preventing photo-catalytic decomposition reaction by binding, generating heat and extinguishing, thereby preventing the reaction from being hindered. Electron (e − )
The agent is not particularly limited as long as it is an agent that becomes an electron acceptor that can prevent recombination between the electron and the hole (h + ).
Potassium bromate (KBrO 3 ), hydrogen peroxide (H 2 O 2 )
And the like, and preferably potassium bromate (KBrO 3 ). The addition amount of the electron receiving material imparting agent is
Although it varies depending on the type of PCB, the amount (concentration) of the PCB-containing liquid, and the like, it is about 10 mmol / l (170 mg / l) based on the total amount of the PCB-containing liquid (PCB concentration 10 mg / l). In the present invention, as a reaction control agent, a pH adjusting agent and an electron acceptor-imparting agent are used in combination, and the PCB-containing liquid is adjusted to pH 7.0 to 7.0.
If it is adjusted to 8.0 and then subjected to photodecomposition processing, PC can be more efficiently
B can be efficiently subjected to photolysis treatment.
【００１３】このように構成される本発明方法では、被
処理液となるＰＣＢ含有液を反応制御剤により調整し、
この調整したＰＣＢ含有液を紫外線の照射下で酸化チタ
ンを用いた光触媒反応によりＰＣＢを光分解処理するの
で、反応の進行と共に、分解物質等の蓄積による酸化チ
タンの光化学活性消失及び反応の停止が防止でき、か
つ、正孔と荷電子の再結合による反応阻害も防止できる
こととなるので、被処理液となるＰＣＢ含有液を効率よ
く、安全に、かつ簡単に光分解処理できるものとなる。
また、本発明方法は、常温、常圧により光触媒反応が行
われるため、他のＰＣＢ分解方法、例えば、燃焼分解法
等と比較して、単純な装置で分解処理を行うことができ
るものである。従って、処理設備を小型化、かつ、移動
式とすることが可能であり、他の処理方法のようにＰＣ
Ｂを輸送することなく分解処理を行うことができる。In the method of the present invention having the above-mentioned structure, the PCB-containing liquid to be treated is adjusted with a reaction control agent.
The PCB containing solution thus prepared is subjected to photodecomposition treatment of the PCB by a photocatalytic reaction using titanium oxide under irradiation of ultraviolet rays. As the reaction progresses, the photochemical activity of titanium oxide is lost due to accumulation of decomposed substances and the reaction is stopped. Since the reaction can be prevented and the reaction inhibition due to the recombination of holes and valence electrons can be prevented, the PCB-containing liquid to be treated can be efficiently, safely, and easily subjected to photodecomposition treatment.
Further, in the method of the present invention, since the photocatalytic reaction is carried out at normal temperature and normal pressure, the decomposition treatment can be carried out with a simple apparatus as compared with other PCB decomposition methods, for example, the combustion decomposition method. . Therefore, it is possible to reduce the size of the processing equipment and to make the processing equipment mobile.
The decomposition treatment can be performed without transporting B.
【００１４】[0014]
【実施例】次に、試験実施例により、本発明を更に説明
するが、本発明は下記試験実施例に限定されるものでは
ない。EXAMPLES Next, the present invention will be further described with reference to test examples, but the present invention is not limited to the following test examples.
【００１５】（試験実施例１）図１に示す光触媒分解装
置１０を使用して置換塩素数の異なるＰＣＢ、具体的に
は、低塩素（２〜３塩素数）置換ＰＣＢ、高塩素（５〜
７塩素数）置換ＰＣＢの分解処理を反応制御剤なしで行
った。すなわち、低塩素（２〜３塩素数）置換ＰＣＢ溶
液１リットル、または、高塩素（５〜７塩素数）置換Ｐ
ＣＢ溶液１リットル、酸化チタン１ｇを処理槽１１内に
収容して分解処理を行った。処理槽１１内に収容された
当初ＰＣＢ含有液のｐＨは、７．０〜８．０であった。
また、紫外線は、波長＜３９０ｎｍの紫外線を照射して
行い、分解処理は、常温（室温下）、常圧で行った。こ
の結果を図３に示す。図３から明らかなように、低塩素
（２〜３塩素数）置換ＰＣＢの場合は、１時間で完全に
分解できることが判明したが、高塩素（５〜７塩素数）
置換ＰＣＢでは６時間後においても完全に分解できない
ことが判明した。Test Example 1 Using the photocatalytic decomposition apparatus 10 shown in FIG. 1, PCBs having different substituted chlorine numbers, specifically, low chlorine (2 to 3 chlorine numbers) substituted PCBs and high chlorine (5 to 5
(7 chlorine number) The decomposition treatment of the substituted PCB was performed without a reaction control agent. That is, 1 liter of low chlorine (2-3 chlorine number) substituted PCB solution or high chlorine (5-7 chlorine number) substituted P
One liter of the CB solution and 1 g of titanium oxide were accommodated in the treatment tank 11 for decomposition. The pH of the PCB-containing liquid initially contained in the processing tank 11 was 7.0 to 8.0.
The ultraviolet rays were irradiated with ultraviolet rays having a wavelength of <390 nm, and the decomposition treatment was performed at normal temperature (under room temperature) and normal pressure. The result is shown in FIG. As is clear from FIG. 3, in the case of the low-chlorine (2-3 chlorine number) -substituted PCB, it was found that the PCB could be completely decomposed in one hour, but high chlorine (5-7 chlorine number).
It was found that the substituted PCB could not be completely decomposed even after 6 hours.
【００１６】（試験実施例２）図１に示す光触媒分解装
置１０を使用してＰＣＢ含有トランス油の分解処理を行
った。すなわち、ＰＣＢ含有トランス油１リットル、酸
化チタン１ｇを処理槽１１内に収容して分解処理を行っ
た。処理槽１１内に収容された当初ＰＣＢ含有液のｐＨ
は、６．３であった。また、紫外線は、高圧水銀灯（波
長＜３９０ｎｍ）を照射して行い、分解処理は、常温
（室温下）、常圧で行った。この結果を図４に示す。図
４から明らかなように、反応の経過と共に、反応液のｐ
Ｈは低下し、ＰＣＢの分解反応が阻害され、ＰＣＢ残存
率は、４時間後からＰＣＢの分解反応が略起こらないこ
とが判明した。(Test Example 2) Using a photocatalytic decomposition apparatus 10 shown in FIG. 1, decomposition treatment of PCB-containing transformer oil was performed. That is, 1 liter of the PCB-containing transformer oil and 1 g of titanium oxide were accommodated in the treatment tank 11 for decomposition. PH of the PCB-containing liquid initially contained in the processing tank 11
Was 6.3. The ultraviolet rays were irradiated with a high-pressure mercury lamp (wavelength <390 nm), and the decomposition treatment was performed at normal temperature (under room temperature) and normal pressure. The result is shown in FIG. As is clear from FIG. 4, as the reaction progresses, the p of the reaction solution increases.
H decreased, and the decomposition reaction of PCB was inhibited, and it was found that the decomposition rate of PCB hardly occurred after 4 hours in the PCB residual ratio.
【００１７】（試験実施例３）図１に示す光触媒分解装
置１０を使用してＰＣＢ含有トランス油の分解処理を反
応制御剤としてｐＨ調製剤（ＮａＯＨ溶液）有無で行っ
た。すなわち、ＰＣＢ含有トランス油１リットル、酸化
チタン１ｇを処理槽１１内に収容し、ｐＨ調製剤の添加
ある場合と添加ない場合における分解処理を行った。処
理槽１１内に収容された当初ＰＣＢ含有液のｐＨは、
６．３であった。なお、ｐＨ調製剤の添加は、ピペット
で添加し、反応液を常時ｐＨ７．０〜７．５の範囲内で
処理した。また、紫外線は、高圧水銀灯（波長＜３９０
ｎｍ）を照射して行い、分解処理は、常温（室温下）、
常圧で行った。この結果を図５に示す。図５から明らか
なように、ｐＨ調製剤の添加ない場合と比較してｐＨ調
製剤の添加ある場合のＰＣＢ残存率は、６時間後で略分
解できることが判明した。(Test Example 3) Using a photocatalytic decomposition apparatus 10 shown in FIG. 1, decomposition treatment of PCB-containing trans oil was carried out with and without a pH adjuster (NaOH solution) as a reaction control agent. That is, 1 liter of the PCB-containing transformer oil and 1 g of titanium oxide were accommodated in the treatment tank 11, and decomposition treatment was performed with and without the addition of the pH adjuster. The pH of the PCB-containing liquid initially contained in the processing tank 11 is:
6.3. The pH adjusting agent was added by a pipette, and the reaction solution was constantly processed within a pH range of 7.0 to 7.5. Ultraviolet rays are emitted from a high-pressure mercury lamp (wavelength <390).
nm) at room temperature (at room temperature),
Performed at normal pressure. The result is shown in FIG. As is clear from FIG. 5, it was found that the PCB remaining rate when the pH adjusting agent was added could be substantially decomposed after 6 hours as compared with the case where the pH adjusting agent was not added.
【００１８】（試験実施例４）図１に示す光触媒分解装
置１０を使用してＣｌ6−ＰＣＢ標準液の分解処理を反
応制御剤としてｐＨ調製剤（ＮａＯＨ）、電子受溶体付
与剤（ＫＢｒＯ3）で行った。すなわち、Ｃｌ6−ＰＣＢ
標準液（１０ｍｇ／ｌ）１リットル、ＮａＯＨ（１％溶
液）、ＫＢｒＯ3１７０ｍｇ（１０ｍｍｏｌ／ｌ）、酸
化チタン１ｇを処理槽１１内に収容して処理を行った。
処理槽１１内に収容された当初ＰＣＢ含有液のｐＨは、
７．５であった。なお、反応液を常時ｐＨ７．０〜８．
０の範囲内で処理した。また、紫外線は、波長＜３９０
ｎｍの紫外線を照射して行い、分解処理は、常温（室温
下）、常圧で行った。この結果を図６に示す。図６から
明らかなように、ｐＨ調製剤（ＮａＯＨ）と電子受溶体
付与剤（ＫＢｒＯ3）とを併用した場合、６時間後で完
全に分解できることが判明した。(Test Example 4) Using a photocatalytic decomposition apparatus 10 shown in FIG. 1 as a reaction control agent to decompose a standard solution of Cl 6 -PCB, a pH adjuster (NaOH), an electron acceptor imparting agent (KBrO 3) ). That is, Cl 6 -PCB
1 liter of a standard solution (10 mg / l), NaOH (1% solution), 170 mg of KBrO 3 (10 mmol / l), and 1 g of titanium oxide were accommodated in the treatment tank 11 for processing.
The pH of the PCB-containing liquid initially contained in the processing tank 11 is:
7.5. In addition, the reaction solution was constantly adjusted to pH 7.0 to 8.0.
Processed within the range of 0. The ultraviolet light has a wavelength of <390.
The decomposition treatment was performed at normal temperature (under room temperature) and normal pressure. The result is shown in FIG. As is clear from FIG. 6, it was found that when the pH adjuster (NaOH) and the electron acceptor-imparting agent (KBrO 3 ) were used in combination, they could be completely decomposed after 6 hours.
【００１９】上記試験実施例１〜４の結果を総合する
と、酸化チタンを用いたＰＣＢの光触媒分解方法におい
て、被処理液となるＰＣＢ含有液を反応制御剤、すなわ
ち、ｐＨ調整剤及び／又は電子受溶付与剤により調整し
てＰＣＢ含有液を紫外線の照射下で光触媒反応を行え
ば、効率よく、安全に、かつ簡単にＰＣＢを光分解処理
できることが判った。When the results of the above Test Examples 1 to 4 are summarized, in the method of photocatalytic decomposition of PCB using titanium oxide, the PCB-containing liquid to be treated is a reaction control agent, that is, a pH adjuster and / or an electronic control agent. It was found that by performing a photocatalytic reaction on the PCB-containing liquid under irradiation with ultraviolet light by adjusting the concentration of the PCB with a solution-imparting agent, it was possible to efficiently, safely, and easily perform a photolysis treatment on PCB.
【００２０】[0020]
【発明の効果】本発明によれば、反応の進行と共に、分
解物質等の蓄積による酸化チタンの光化学活性消失及び
反応の停止が防止でき、かつ、正孔と荷電子の再結合に
よる反応阻害も防止できるので、被処理液となるＰＣＢ
含有液を効率よく、安全に、かつ簡単に光分解処理でき
るものとなる。また、本発明方法は、常温、常圧により
光触媒反応が行うことができるので、単純な装置で分解
処理を行うことができる。従って、処理設備を小型化、
かつ、移動式とすることができ、他の処理方法のように
ＰＣＢを輸送することなく分解処理を行うことができ
る。According to the present invention, the loss of photochemical activity of titanium oxide due to the accumulation of decomposed substances and the termination of the reaction can be prevented with the progress of the reaction, and the reaction is inhibited by the recombination of holes and valence electrons. PCB that can be treated because it can be prevented
The contained solution can be efficiently, safely, and easily subjected to photolysis treatment. Further, in the method of the present invention, the photocatalytic reaction can be performed at normal temperature and normal pressure, so that the decomposition treatment can be performed with a simple device. Therefore, the processing equipment can be downsized,
In addition, it can be of a mobile type, and the decomposition treatment can be performed without transporting the PCB unlike other treatment methods.
【図１】本発明方法における光触媒酸化分解反応の機構
を説明する説明図である。FIG. 1 is an explanatory diagram illustrating the mechanism of a photocatalytic oxidative decomposition reaction in the method of the present invention.
【図２】本発明方法に用いる光触媒分解装置の一例を示
す概略図である。FIG. 2 is a schematic diagram showing an example of a photocatalytic decomposition device used in the method of the present invention.
【図３】置換塩素数の異なるＰＣＢ含有液のＰＣＢ分解
率を示す特性図である。FIG. 3 is a characteristic diagram showing the PCB decomposition rates of PCB-containing liquids having different substituted chlorine numbers.
【図４】ＰＣＢ含有トランス油における分解率とｐＨの
関係を示す特性図である。FIG. 4 is a characteristic diagram showing a relationship between a decomposition rate and a pH in a PCB-containing transformer oil.
【図５】反応制御剤（ｐＨ調整剤）によるＰＣＢ分解率
を示す特性図である。FIG. 5 is a characteristic diagram showing a PCB decomposition rate by a reaction control agent (pH adjusting agent).
【図６】Ｃｌ6−ＰＣＢ標準液のＰＣＢ分解率を示す特
性図である。FIG. 6 is a characteristic diagram showing a PCB decomposition rate of a Cl 6 -PCB standard solution.
１０ 光触媒分解装置 １１ 処理槽 10 Photocatalytic decomposition device 11 Processing tank
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０２Ｆ 1/72 １０１ Ｃ０２Ｆ 1/72 １０１ ４Ｈ００６ Ｃ０７Ｂ 35/06 Ｃ０７Ｂ 35/06 37/06 37/06 Ｃ０７Ｃ 25/18 Ｃ０７Ｃ 25/18 // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ (72)発明者 武尾 正弘 兵庫県姫路市梅ヶ谷町５−10 Ｆターム(参考） 2E191 BA13 BC01 BD13 BD17 4D037 AA13 AB14 BA18 BB01 BB09 CA12 CA14 4D038 AA10 AB01 AB14 BA02 BA06 BB07 BB16 4D050 AA13 AB19 BB01 BC06 BC09 CA07 CA13 4G069 AA02 BA04A BA04B BA48A CA01 CA10 CA19 4H006 AA02 AC13 BA02 BA10 BA30 BA37 BA95 BC16 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C02F 1/72 101 C02F 1/72 101 4H006 C07B 35/06 C07B 35/06 37/06 37/06 C07C 25 / 18 C07C 25/18 // C07B 61/00 300 C07B 61/00 300 (72) Inventor Masahiro Takeo 5-10 Umegaya-cho, Himeji-shi, Hyogo F-term (reference) 2E191 BA13 BC01 BD13 BD17 4D037 AA13 AB14 BA18 BB01 BB09 CA12 CA14 4D038 AA10 AB01 AB14 BA02 BA06 BB07 BB16 4D050 AA13 AB19 BB01 BC06 BC09 CA07 CA13 4G069 AA02 BA04A BA04B BA48A CA01 CA10 CA19 4H006 AA02 AC13 BA02 BA10 BA30 BA37 BA95 BC16
Claims (5)
方法であって、被処理液となるＰＣＢ含有液を反応制御
剤により調整し、この調整したＰＣＢ含有液を紫外線の
照射下で光触媒反応によりＰＣＢを光分解処理すること
を特徴とするＰＣＢの光触媒分解方法。1. A method for photocatalytic decomposition of PCB using titanium oxide, wherein a PCB-containing liquid to be treated is adjusted with a reaction control agent, and the adjusted PCB-containing liquid is subjected to a photocatalytic reaction under irradiation of ultraviolet rays. A photocatalytic decomposition method for PCB, comprising subjecting PCB to photolysis treatment.
Ｈ調製剤により、ＰＣＢ含有液をｐＨ７．０〜８．０に
調整しながら光分解処理する請求項１記載のＰＣＢの光
触媒分解方法。2. A reaction control agent comprising a pH adjuster,
The method for photocatalytic decomposition of PCB according to claim 1, wherein the PCB-containing liquid is subjected to a photolysis treatment while adjusting the pH to 7.0 to 8.0 with an H preparation agent.
請求項１記載のＰＣＢの光触媒分解方法。3. The method for photocatalytic decomposition of PCB according to claim 1, wherein the reaction control agent comprises an electron receiving material imparting agent.
なる請求項３記載のＰＣＢの光触媒分解方法。4. The method for photocatalytic decomposition of PCB according to claim 3, wherein the electron acceptor-imparting agent comprises potassium bromate.
溶体付与剤とを併用し、該ｐＨ調製剤により、ＰＣＢ含
有液をｐＨ７．０〜８．０に調整しながら光分解処理す
る請求項１又は４記載のＰＣＢの光触媒分解方法。5. A photo-decomposition treatment using a pH adjuster and an electron acceptor-imparting agent in combination as a reaction control agent, and adjusting the pH of the PCB-containing solution to pH 7.0 to 8.0 with the pH adjuster. Item 5. The photocatalytic decomposition method of PCB according to item 1 or 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11208162A JP2001029942A (en) | 1999-07-22 | 1999-07-22 | Photocatalytic decomposition method of pcb |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11208162A JP2001029942A (en) | 1999-07-22 | 1999-07-22 | Photocatalytic decomposition method of pcb |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001029942A true JP2001029942A (en) | 2001-02-06 |
Family
ID=16551691
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11208162A Pending JP2001029942A (en) | 1999-07-22 | 1999-07-22 | Photocatalytic decomposition method of pcb |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001029942A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012005937A (en) * | 2010-06-23 | 2012-01-12 | Toshio Konuma | System for treating waste electrical equipment contaminated with pcb |
-
1999
- 1999-07-22 JP JP11208162A patent/JP2001029942A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012005937A (en) * | 2010-06-23 | 2012-01-12 | Toshio Konuma | System for treating waste electrical equipment contaminated with pcb |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2015282298B2 (en) | Method for manufacturing reaction product in which phase interface reaction is employed, phase interface reactor, and method for manufacturing secondary reaction product | |
| EP2263795A1 (en) | Photocatalyst, preparation method thereof, photoreactor, and photolysis process | |
| US5124051A (en) | Process for treatment of contaminated waste water or groundwater | |
| ATE227360T1 (en) | HEAT EXCHANGER WITH REDUCED TENDENCE TO FORM DEPOSITS AND METHOD FOR PRODUCING THE SAME | |
| Krupež et al. | Degradation of nicotine in water solutions using a water falling film DBD plasma reactor: direct and indirect treatment | |
| US20070095647A1 (en) | Method and apparatus for producing reactive oxidizing species | |
| US5798047A (en) | Process and apparatus for ultraviolet decomposition of waste water containing organic substances | |
| Park et al. | Degradation of polycyclic aromatic hydrocarbons by ultrasonic irradiation | |
| Sapach et al. | An introduction to the use of hydrogen peroxide and ultraviolet radiation: An advanced oxidation process | |
| JP2001029942A (en) | Photocatalytic decomposition method of pcb | |
| Li et al. | Treatment of azole-containing industrial wastewater by the fenton process | |
| Matějka et al. | Mechanisms leading to plasma activated water high in nitrogen oxides | |
| JP2002177775A (en) | Visible ray reaction type photocatalyst and manufacturing method thereof | |
| Choy et al. | The modelling of trichloroethene photodegradation in Brij 35 surfactant by two-stage reaction | |
| JP2000202466A (en) | Treatment of sewage containing internal secretion disturbance material or carcinogenic substance and its apparatus | |
| JP3554857B2 (en) | Water treatment method using photocatalyst | |
| US6767472B2 (en) | Catalytic fixed bed reactor systems for the destruction of contaminants in water by hydrogen peroxide and ozone | |
| JP2000288536A (en) | Method and apparatus for treating waste water containing hydrogen peroxide | |
| JP2003053359A (en) | Method for cleaning liquid polluted with pcb | |
| DeMers et al. | Alternative disinfection technologies for small systems | |
| JP2010022958A (en) | Photolysis method | |
| US20030034311A1 (en) | Catalytic fixed bed reactor systems for the destruction of contaminants in water by hydrogen peroxide and ozone | |
| KR970011329B1 (en) | Tert-butyalcohol decomposing method using gamma rays, ozone and heavy metal | |
| JP3917713B2 (en) | Method for decomposing polychlorinated biphenyls in oil | |
| CN112158909A (en) | Method for treating tetracycline in water by using UV activated double-oxidant system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20040809 |