JPH11277064A - Fixed bed type three-dimensional electrode, fixed bed type three dimensional electrode electrolytic bath, and water treatment method - Google Patents
Fixed bed type three-dimensional electrode, fixed bed type three dimensional electrode electrolytic bath, and water treatment methodInfo
- Publication number
- JPH11277064A JPH11277064A JP8130298A JP8130298A JPH11277064A JP H11277064 A JPH11277064 A JP H11277064A JP 8130298 A JP8130298 A JP 8130298A JP 8130298 A JP8130298 A JP 8130298A JP H11277064 A JPH11277064 A JP H11277064A
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- Prior art keywords
- bed type
- fixed
- dimensional electrode
- electrolytic cell
- electrode
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は被処理水たとえば微
生物を含有する被処理水を電気化学的に処理するための
固定床型三次元電極に関し、より効果的な被処理水の処
理を行う複極式固定床型三次元電極電解槽に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fixed-bed type three-dimensional electrode for electrochemically treating water to be treated, for example, water containing microorganisms. The present invention relates to a pole type fixed bed type three-dimensional electrode electrolytic cell.
【０００２】[0002]
【従来の技術】現在、我々が生活をする上で様々な種類
の水が使用されている。例えば、井戸水、水道水、工業
用水、純水、超純水、浴槽水、プール水などである。
又、使用された水は工業排水或いは生活排水となる。或
いは、各種産業においていろいろな物質を含有する水が
利用されている。これらの水溶液等は溶質が適度な養分
を提供し、或いは該水溶液の液温が繁殖に好ましい温度
であると、細菌等の微生物が繁殖し、前記水等の性能劣
化を起こしたり、様々な悪影響を及ぼすことが知られて
いる。また、工場排水などには様々な不純物が含まれて
おり、環境汚染防止のための不純物除去或いは有用物質
の回収が行われている。2. Description of the Related Art At present, various kinds of water are used in our daily lives. For example, well water, tap water, industrial water, pure water, ultrapure water, bathtub water, pool water, etc.
The used water is industrial wastewater or domestic wastewater. Alternatively, water containing various substances is used in various industries. If these solutes provide appropriate nutrients, or if the temperature of the aqueous solution is a preferable temperature for propagation, microorganisms such as bacteria will propagate and cause deterioration of the performance of the water and various adverse effects. It is known to exert Furthermore, various impurities are contained in factory wastewater and the like, and impurities are removed or useful substances are collected to prevent environmental pollution.
【０００３】例えば写真感光材料は画像露光の後、ペー
パー感光材料処理の場合は、発色現像、漂白定着、水洗
及び／又は安定化の処理工程を経て処理され次いで乾燥
される。そしてこのような写真処理工程においては、発
色現像液、漂白液、漂白定着液、定着液、安定液、水洗
水等の各種写真処理液が使用されているが、前記感光材
料はゼラチン質を含有し微生物繁殖に適した環境を提供
するため、前記写真処理液中に混入した微生物が繁殖し
て感光材料処理の効率を低下させるとともに得られるプ
リントに色むらが生じたり黴発生等により画像が汚染す
るという欠点が生じている。この微生物繁殖による写真
処理液の劣化の抑制は、従来から防黴剤の投入等により
前記微生物を殺菌して性能を賦活する方法が主流である
が、この方法では添加する防黴剤が多量に必要となり、
かつ該防黴剤が写真処理液や前記感光材料中に残留し易
くなり、感光材料に悪影響を及ぼすことがある。又前記
防黴剤の多くは人体に対して無害とは言い難く、種々の
法規制の下に管理された状態でなければその使用が困難
である。又このように選択した防黴剤も暫くするとその
防黴剤に対する抗菌が発生することがあり、再度この抗
菌に対して防黴剤を選択するという煩わしい問題が生ず
る。[0003] For example, a photographic light-sensitive material is processed after image exposure, in the case of paper light-sensitive material processing, through color developing, bleach-fixing, washing and / or stabilizing processing steps, and then dried. In such a photographic processing step, various photographic processing solutions such as a color developing solution, a bleaching solution, a bleach-fixing solution, a fixing solution, a stabilizing solution, and washing water are used, but the photosensitive material contains a gelatinous material. In order to provide an environment suitable for the propagation of microorganisms, microorganisms mixed in the photographic processing solution proliferate and reduce the efficiency of processing of the photosensitive material. The drawback is that it does. In order to suppress the deterioration of the photographic processing solution due to the propagation of microorganisms, a method of activating the performance by sterilizing the microorganisms by adding a fungicide or the like has conventionally been the mainstream, but in this method, a large amount of the fungicide to be added is used. Required
In addition, the fungicide tends to remain in the photographic processing solution or the light-sensitive material, which may adversely affect the light-sensitive material. Many of the fungicides are not harmless to the human body, and it is difficult to use them unless they are managed under various laws and regulations. Also, the antifungal agent thus selected may cause antibacterial action against the antifungal agent after a while, and the troublesome selection of the antifungal agent against this antifungal agent occurs again.
【０００４】また、プールに使用される水には人体に有
害な細菌類等の微生物が数多く生息し、該プール水は利
用者の眼や傷などに直接接触して疾患を生じさせる可能
性が高いため、プール水には次亜塩素酸ソーダ等の薬剤
を投入して消毒を行って疾患の発生を防止している。し
かしながら前記薬剤として殺菌効果の強い次亜塩素酸や
液体塩素等の塩素系試薬が使用され、該塩素系試薬はそ
れ自体或いは分解物が刺激性を有し、該試薬により殺菌
等の効果が生じても、該試薬による眼の痛みや皮膚のか
ぶれ等の副作用が発生し、特に抵抗力の弱い幼児の場合
は大きな問題となっている。[0004] In addition, a large amount of microorganisms such as bacteria harmful to the human body inhabit the water used for the pool, and the pool water may cause direct contact with the eyes and wounds of the user to cause diseases. Due to the high cost, chemicals such as sodium hypochlorite are added to the pool water to disinfect and prevent the occurrence of disease. However, a chlorine-based reagent having a strong bactericidal effect, such as hypochlorous acid or liquid chlorine, is used as the drug, and the chlorine-based reagent itself or a decomposed product has an irritating property, and the reagent produces an effect such as sterilization. Even so, side effects such as eye pain and skin irritation occur due to the reagent, and this is a serious problem particularly for infants with low resistance.
【０００５】また近年の情報化社会の進展により各種紙
類特に高質紙の需要が増大している。この紙類は製紙用
パルプから各種工程を経て製造されるが、この工程中に
製紙前のパルプを洗浄して不要な成分を洗い流す工程が
ある。該パルプは適度な温度に維持されかつ適度な養分
を含むため、黴や細菌等の微生物が繁殖し易くこの黴や
細菌が多量に最終製品中に残存すると、紙類の褪色等の
性能の劣化が生ずる。従ってこの洗浄工程で使用される
莫大な量の洗浄水中には、防黴剤や殺菌剤が含有され最
終製品の性能劣化を極力防止するようにしている。しか
しこの方法では、防黴剤や殺菌剤のコストが高くなるだ
けでなく前記防黴剤や殺菌剤が製品中に残存して黴や細
菌類に起因する性能劣化とは別の性能劣化を来すことが
あるという問題点がある。[0005] Further, with the recent development of the information-oriented society, demand for various kinds of paper, especially high-quality paper, has been increasing. This paper is manufactured from pulp for papermaking through various processes. In this process, there is a process of washing pulp before papermaking to wash away unnecessary components. Since the pulp is maintained at an appropriate temperature and contains an appropriate amount of nutrients, microorganisms such as molds and bacteria easily proliferate, and when a large amount of the molds and bacteria remain in the final product, deterioration of performance such as discoloration of papers. Occurs. Therefore, an enormous amount of washing water used in this washing step contains a fungicide and a bactericide to prevent performance deterioration of the final product as much as possible. However, this method not only increases the cost of the fungicide and fungicide, but also causes the fungicide and fungicide to remain in the product, resulting in performance degradation different from the performance degradation caused by molds and bacteria. There is a problem that sometimes.
【０００６】又、様々な製造業において、純水や工業用
水などが使用されている。洗浄工程で使用された水には
様々な有機物が混入するため、これが適度な養分を提供
し、特に該水溶液の液温が微生物の繁殖に好ましい温度
になると、細菌等の微生物が繁殖して製品の性能劣化を
起こしたり処理装置内に浮遊したり蓄積し、水の再利用
を困難にしている。[0006] In various manufacturing industries, pure water, industrial water and the like are used. Since various organic substances are mixed in the water used in the washing process, this provides an appropriate nutrient, and especially when the liquid temperature of the aqueous solution reaches a temperature suitable for the propagation of microorganisms, microorganisms such as bacteria grow and the product The performance of the water is deteriorated, and the water floats or accumulates in the processing apparatus, making it difficult to reuse water.
【０００７】例えば、半導体あるいはプリント基板の製
造においては多量の純水あるいは超純水が洗浄工程で使
用されているが、工業用水から純水あるいは超純水を作
るとコストがかかるため、通常洗浄排水をリサイクルし
て使用している。しかしながら、洗浄工程から持ち込ま
れる有機物などのため、細菌などの微生物が繁殖し、そ
のため製品の性能劣化を起こしたり、再生工程の負荷を
増加させていた。For example, in the production of semiconductors or printed circuit boards, a large amount of pure water or ultrapure water is used in the cleaning step. However, it is costly to produce pure water or ultrapure water from industrial water. Wastewater is recycled and used. However, microorganisms such as bacteria proliferate due to organic substances and the like brought in from the washing step, thereby deteriorating the performance of the product and increasing the load on the regeneration step.
【０００８】ところで、環境汚染の問題もなく、低コス
トで容易に活性酸素を発生させる方法として、ポリアニ
リンを用いた活性酸素発生法が特開平９−１７５８０１
号に開示されている。導電性高分子であるポリアニリン
を酸素を含有する水に接触させると、ポリアニリンが水
中の溶存酸素を活性化させて活性酸素を発生させる。そ
こで、ポリアニリンを被処理水に添加することにより殺
菌を行う方法が提示されている。As a method for easily generating active oxygen at a low cost without a problem of environmental pollution, an active oxygen generation method using polyaniline is disclosed in Japanese Patent Laid-Open No. Hei 9-175801.
Issue. When polyaniline, which is a conductive polymer, is brought into contact with water containing oxygen, the polyaniline activates dissolved oxygen in the water to generate active oxygen. Thus, a method of sterilizing by adding polyaniline to the water to be treated has been proposed.
【０００９】また大塚らによる１９９７年材料技術ｖｏ
ｌ．１５，Ｎｏ．５によると負の電圧を印加し、常にポ
リアニリンを還元することにより連続的な活性酸素の発
生を行うことができると示されている。[0009] Otsuka et al., 1997, Material Technology vo
l. 15, No. According to No. 5, it is shown that continuous generation of active oxygen can be performed by applying a negative voltage and constantly reducing polyaniline.
【００１０】しかし、活性酸素はその寿命が短いことか
ら被処理水を活性酸素発生装置に数分から数十分とどめ
ておく必要がある。そのため、論文中の装置では大流量
での連続的な処理は困難であった。However, since the active oxygen has a short life, it is necessary to keep the water to be treated in the active oxygen generator for several minutes to several tens of minutes. For this reason, continuous processing at a large flow rate was difficult with the apparatus described in the paper.
【００１１】我々は、水処理法として、例えば特開平３
−２２４６８６号、同４−２７４８８号等に開示されて
いる、電気化学的に処理する方法を検討してきた。この
方法によると、特殊な薬品等を使わず、大量の水を効率
よく処理することができる。上記水処理装置における複
極式固定床型三次元電極電解槽の電極は、陽極、陰極に
分極され、該電極上では電極に付着あるいは接触した微
生物は、主に陽極で失活あるいは殺菌されていると考え
られる。As a water treatment method, for example, Japanese Unexamined Patent Publication No.
Nos. 224686 and 4-27488, etc., have been studied for electrochemical treatment. According to this method, a large amount of water can be efficiently treated without using a special chemical or the like. The electrode of the bipolar fixed bed type three-dimensional electrode electrolytic cell in the water treatment apparatus is polarized to an anode and a cathode, and microorganisms attached to or in contact with the electrode on the electrode are mainly inactivated or sterilized by the anode. It is thought that there is.
【００１２】[0012]
【発明が解決しようとする課題】本発明は固定床型三次
元電極電解槽を用いる被処理水中の微生物を電気化学的
に処理する方法において、より効果的な大量、連続処理
可能な殺菌方法を提供することにある。SUMMARY OF THE INVENTION The present invention relates to a method for electrochemically treating microorganisms in water to be treated using a fixed-bed type three-dimensional electrode electrolytic cell. To provide.
【００１３】[0013]
【課題を解決するための手段】本発明の上記目的は、下
記構成により達成された。The above objects of the present invention have been attained by the following constitutions.
【００１４】（１） 被処理水を電気化学的に処理する
固定床型三次元電極電解槽に用いられる固定床型三次元
電極が、活性酸素発生剤を担持することを特徴とする固
定床型三次元電極。(1) The fixed-bed type three-dimensional electrode used in the fixed-bed type three-dimensional electrode electrolytic cell for electrochemically treating the water to be treated carries an active oxygen generating agent. Three-dimensional electrode.
【００１５】（２） 活性酸素発生剤を担持させる固定
床型三次元電極の材質がグラファイト、グラッシーカー
ボン、活性炭素等の炭素系材料又は金属であることを特
徴とする前記１記載の固定床型三次元電極。(2) The fixed-bed type three-dimensional electrode for supporting an active oxygen generator is made of a carbon-based material such as graphite, glassy carbon, or activated carbon or a metal, or a metal. Three-dimensional electrode.
【００１６】（３） 前記１又は２記載の固定床型三次
元電極を少なくとも一つ有することを特徴とする固定床
型三次元電極電解槽。(3) A fixed-bed type three-dimensional electrode electrolytic cell comprising at least one fixed-bed type three-dimensional electrode as described in (1) or (2) above.
【００１７】（４） 固定床型三次元電極電解槽におい
て、前記１又は２記載の固定床型三次元電極の陽極部分
に、０．７Ｖ（ｖｓ．ＳＣＥ）以上の電位を印加するこ
とを特徴とする固定床型三次元電極電解槽。(4) In the fixed-bed type three-dimensional electrode electrolytic cell, a potential of 0.7 V (vs. SCE) or more is applied to the anode part of the fixed-bed type three-dimensional electrode described in 1 or 2 above. Fixed-bed type three-dimensional electrode electrolytic cell.
【００１８】（５） 固定床型三次元電極電解槽におい
て、前記１又は２記載の固定床型三次元電極の陰極部分
に、−０．１Ｖ（ｖｓ．ＳＣＥ）以下の電位を印加する
ことを特徴とする固定床型三次元電極電解槽。(5) In the fixed-bed type three-dimensional electrode electrolytic cell, applying a potential of -0.1 V (vs. SCE) or less to the cathode portion of the fixed-bed type three-dimensional electrode described in 1 or 2 above. Characteristic fixed-bed type three-dimensional electrode electrolytic cell.
【００１９】（６） 固定床型三次元電極電解槽におい
て、印加する電圧の正負を一定時間毎に反転することを
特徴とする前記３〜５のいずれか１項記載の固定床型三
次元電極電解槽。(6) The fixed-bed three-dimensional electrode according to any one of (3) to (5), wherein in the fixed-bed three-dimensional electrode electrolytic cell, the polarity of the applied voltage is reversed at regular intervals. Electrolyzer.
【００２０】（７） 前記３〜６のいずれか１項記載の
固定床型三次元電極電解槽を用いることを特徴とする水
処理方法。(7) A water treatment method comprising using the fixed-bed type three-dimensional electrode electrolytic cell according to any one of (3) to (6).
【００２１】（８） 被処理水に過酸化水素を添加する
ことを特徴とする前記７記載の水処理方法。(8) The water treatment method according to the above (7), wherein hydrogen peroxide is added to the water to be treated.
【００２２】（９） 固定床型三次元電極の陰極となる
側に活性酸素発生剤を担持させることを特徴とする固定
床型三次元電極。(9) A fixed bed type three-dimensional electrode characterized in that an active oxygen generating agent is carried on the cathode side of the fixed bed type three-dimensional electrode.
【００２３】（１０） 活性酸素発生剤を担持させる固
定床型三次元電極の材質が炭素質又は金属からなること
を特徴とする前記９記載の固定床型三次元電極。(10) The fixed-bed type three-dimensional electrode according to the above item 9, wherein the material of the fixed-bed type three-dimensional electrode for supporting an active oxygen generating agent is made of carbon or metal.
【００２４】（１１） 前記９又は１０記載の固定床型
三次元電極を少なくとも一つ有することを特徴とする固
定床型三次元電極電解槽。(11) A fixed-bed type three-dimensional electrode electrolytic cell comprising at least one fixed-bed type three-dimensional electrode according to the item (9) or (10).
【００２５】（１２） 固定床型三次元電極電解槽にお
いて、前記９又は１０記載の固定床型三次元電極の陽極
部分に、０．７Ｖ（ｖｓ．ＳＣＥ）以上の電位を印加す
ることを特徴とする固定床型三次元電極電解槽。(12) In the fixed-bed type three-dimensional electrode electrolytic cell, a potential of 0.7 V (vs. SCE) or more is applied to the anode part of the fixed-bed type three-dimensional electrode described in 9 or 10 above. Fixed-bed type three-dimensional electrode electrolytic cell.
【００２６】（１３） 固定床型三次元電極電解槽にお
いて、前記９又は１０記載の固定床型三次元電極の陰極
部分に、−０．１Ｖ（ｖｓ．ＳＣＥ）以下の電位を印加
することを特徴とする固定床型三次元電極電解槽。(13) In the fixed-bed type three-dimensional electrode electrolytic cell, applying a potential of -0.1 V (vs. SCE) or less to the cathode portion of the fixed-bed type three-dimensional electrode described in 9 or 10 above. Characteristic fixed-bed type three-dimensional electrode electrolytic cell.
【００２７】（１４） 固定床型三次元電極電解槽にお
いて、印加する電圧の正負を反転しないことを特徴とす
る前記１１〜１３のいずれか１項記載の固定床型三次元
電極電解槽。(14) The fixed-bed type three-dimensional electrode electrolytic cell according to any one of (11) to (13), wherein the polarity of the applied voltage is not reversed in the fixed-bed type three-dimensional electrode electrolytic cell.
【００２８】（１５） 前記１１〜１４のいずれか１項
記載の固定床型三次元電極電解槽を用いることを特徴と
する水処理方法。(15) A water treatment method comprising using the fixed-bed type three-dimensional electrode electrolytic cell according to any one of (11) to (14).
【００２９】（１６） 被処理水が電導度５μＳ／ｃｍ
以下のイオン交換水であることを特徴とする前記１５記
載の水処理方法。(16) The water to be treated has an electric conductivity of 5 μS / cm
16. The water treatment method according to the above 15, wherein the water is the following ion-exchanged water.
【００３０】本発明の固定床型三次元電極電解槽は一対
の給電用板状電極好ましくはメッシュ状の電極間に１以
上好ましくは３〜１５の固定床型三次元電極を配置し、
前記の一対の給電用電極に電圧を印加することによっ
て、固定床型三次元電極を分極させ、この固定床に処理
水を通して、電気化学的に、または活性酸素により、細
菌、ウィルス、原虫などの微生物の除去・殺菌する水処
理装置である。In the fixed-bed type three-dimensional electrode electrolytic cell of the present invention, one or more, preferably 3 to 15, preferably three to fifteen fixed-bed type three-dimensional electrodes are arranged between a pair of plate-like electrodes for power supply, preferably mesh electrodes.
By applying a voltage to the pair of power supply electrodes, the fixed-bed type three-dimensional electrode is polarized, and treated water is passed through the fixed bed, electrochemically or by active oxygen, thereby causing bacteria, viruses, protozoa, etc. This is a water treatment device that removes and sterilizes microorganisms.
【００３１】固定床型三次元電極殺菌装置の殺菌原理は
様々な作用が相互に影響しているが、そのうちの一つと
して、多孔質電極に微生物が接触した際の微生物−電極
間の直接反応による殺菌が考えられる。The sterilization principle of the fixed-bed type three-dimensional electrode sterilization apparatus is influenced by various actions. One of them is a direct reaction between the microorganism and the electrode when the microorganism contacts the porous electrode. Sterilization is possible.
【００３２】固定床型三次元電極電解槽内には１枚以上
の固定床型三次元電極が入り、三次元固定床電極の両端
に配置した給電用電極に電圧を印加すると電極の両端が
陽極と陰極に分極する。微生物−電極の反応による殺菌
は陽極上で起こることがわかっている。そのため、陰極
に分極した電極上では接触あるいは付着した微生物と電
極との直接反応による殺菌は生じない。One or more fixed-bed type three-dimensional electrodes are placed in the fixed-bed type three-dimensional electrode electrolytic cell. When a voltage is applied to the power supply electrodes disposed at both ends of the three-dimensional fixed-bed electrode, both ends of the electrode become anodes. And polarized to the cathode. Sterilization by microbial-electrode reactions has been found to occur on the anode. Therefore, sterilization by a direct reaction between the contacted or adhered microorganisms and the electrode does not occur on the electrode polarized to the cathode.
【００３３】実際の固定床型三次元電極電解槽による被
処理水の処理においては、電極上への水中の金属イオン
の析出によるスケールの付着防止のために一定時間で印
加電圧の極性を反転させている。そのため、固定床型三
次元電極の分極部分も正負に反転していることになり、
電極上に吸着した微生物はほとんど殺菌されることにな
る。In the actual treatment of the water to be treated by the fixed-bed type three-dimensional electrode electrolytic cell, the polarity of the applied voltage is reversed for a certain period of time in order to prevent scale adhesion due to precipitation of metal ions in the water on the electrodes. ing. Therefore, the polarized part of the fixed-bed type three-dimensional electrode is also inverted to positive and negative,
Most of the microorganisms adsorbed on the electrodes will be killed.
【００３４】しかし、分極した電極の陰極部分での殺菌
が行われていないため、単位時間当たりの殺菌効率は総
電極面積の約半分となってしまう。However, since sterilization is not performed at the cathode portion of the polarized electrode, the sterilization efficiency per unit time is about half of the total electrode area.
【００３５】そこで、陰極部分を有効利用するために鋭
意検討を重ねた結果、固定床型三次元電極に活性酸素発
生剤を担持させることによって、陰極、陽極とも有効に
殺菌に利用できることを見いだした。しかも、驚くべき
事に殺菌効果の著しい向上を見いだすことができたので
ある。Therefore, as a result of intensive studies to effectively use the cathode portion, it was found that by supporting an active oxygen generator on a fixed-bed type three-dimensional electrode, both the cathode and anode can be effectively used for sterilization. . Moreover, surprisingly, a remarkable improvement in the bactericidal effect was found.
【００３６】本発明では固定床型三次元電極に活性酸素
発生剤を担持させる。活性酸素発生剤としては酸素に対
して電子を供与しうるものであればよい。例えばポリア
ニリン、ポリピロールのような導電性高分子やメチレン
ブルー、クロロフィルのような色素、光触媒などを含有
するものである。しかし、ポリアニリンのように紫外線
照射なしで、水と接触しただけで活性酸素を発生させる
ようなものが特に好ましい。In the present invention, an active oxygen generator is supported on a fixed-bed type three-dimensional electrode. Any active oxygen generator may be used as long as it can donate electrons to oxygen. For example, it contains a conductive polymer such as polyaniline or polypyrrole, a dye such as methylene blue or chlorophyll, or a photocatalyst. However, those which generate active oxygen only by contacting with water without ultraviolet irradiation, such as polyaniline, are particularly preferable.
【００３７】活性酸素発生剤の担持は常法に従えばよ
く、例えば導電性高分子の担持は電解質とモノマー物質
を溶かした溶媒中に電極を挿入し、電極上に電解重合さ
せる。あるいは、あらかじめ重合した導電性高分子を電
極上に塗布する。または電極上に触媒を塗布し、これを
ガス状のモノマー物質にさらし、導電性高分子を担持さ
せる等の方法がある。The loading of the active oxygen generating agent may be carried out according to a conventional method. For example, the loading of a conductive polymer is carried out by inserting an electrode into a solvent in which an electrolyte and a monomer substance are dissolved, and electrolytically polymerizing the electrode. Alternatively, a conductive polymer that has been polymerized in advance is applied on the electrode. Alternatively, there is a method of applying a catalyst on the electrode, exposing the catalyst to a gaseous monomer substance, and supporting a conductive polymer.
【００３８】特にポリアニリンは陰極に配置することに
よって連続的に活性酸素を発生させることが可能であ
る。しかしながら一般的に活性酸素の寿命は短く、ある
いは発生量もそれほど多くはないため、効率的に殺菌に
利用することは困難であった。そこで、固定床型三次元
電極に活性酸素発生剤を担持させ、固定床型三次元電極
電解槽を作製し、殺菌効率を調べたところ、著しい殺菌
効率の向上が認められたのである。これは陽極上での殺
菌、陰極上の活性酸素発生剤による活性酸素の発生、そ
して陰極又はその近傍に吸着されている微生物の失活・
殺菌によるものと推測される。ただ、予想以上の殺菌効
率の向上は水の電気分解により陽極上で酸素が発生し、
これが陰極上の活性酸素発生剤の活性酸素発生に寄与し
たものと推察される。In particular, it is possible to continuously generate active oxygen by arranging polyaniline on the cathode. However, in general, the life of active oxygen is short or the amount of generated active oxygen is not so large, so that it has been difficult to efficiently use it for sterilization. Therefore, a fixed-bed three-dimensional electrode was made to carry an active oxygen generating agent, and a fixed-bed three-dimensional electrode electrolytic cell was prepared. When the sterilization efficiency was examined, a remarkable improvement in the sterilization efficiency was found. This involves sterilization on the anode, generation of active oxygen by the active oxygen generator on the cathode, and inactivation of microorganisms adsorbed on or near the cathode.
It is presumed to be due to sterilization. However, the unexpected improvement in sterilization efficiency is due to the generation of oxygen on the anode by electrolysis of water,
This is presumed to have contributed to the active oxygen generation of the active oxygen generator on the cathode.
【００３９】本発明で活性酸素発生剤を担持させる固定
床型三次元電極は、例えば粒状、球状、フェルト状、織
布状、多孔質ブロック状等の形状を有する活性炭、グラ
ファイト、グラッシーカーボン、炭素繊維等の炭素系材
料から、あるいは同形状を有するニッケル、銅、ステン
レス、鉄、チタン等の金属材料、更にそれら金属材料に
貴金属コーティングを施した材料から形成された複数個
の好ましくは粒状、球状、繊維状、フェルト状、織布
状、多孔質ブロック状、スポンジ状の誘電体である。In the present invention, the fixed-bed type three-dimensional electrode for supporting an active oxygen generating agent is, for example, activated carbon, graphite, glassy carbon, carbon, or the like having a granular, spherical, felt, woven or porous block shape. A plurality of preferably granular, spherical, and other materials formed from carbon-based materials such as fibers, or metal materials having the same shape, such as nickel, copper, stainless steel, iron, and titanium, and a material obtained by applying a noble metal coating to those metal materials. , Fibrous, felt, woven, porous block, and sponge dielectrics.
【００４０】微生物の大きさは通常１〜数１０μｍ程度
である。多孔質電極を微生物の混入した被処理水が通過
する際、微生物は電極に接触することが好ましい。従っ
て、該電極が多孔質体である場合、電極及び活性酸素と
の接触距離、目詰まり防止を考慮し、その孔径は１０〜
５００μｍであることが好ましい。The size of the microorganism is usually about 1 to several tens μm. When water to be treated mixed with microorganisms passes through the porous electrode, the microorganisms preferably contact the electrode. Therefore, when the electrode is a porous body, the pore diameter is 10 to 10 in consideration of the contact distance between the electrode and active oxygen and prevention of clogging.
Preferably it is 500 μm.
【００４１】本発明の固定床型三次元電極を図１により
説明する。図１は固定床型三次元電極の縦断面図である
が、図１（ａ）は炭素質又は金属の固定床型三次元電極
１を示す。図１（ｂ）は炭素質又は金属の固定床型三次
元電極１と活性酸素発生剤担持固定床型三次元電極２を
組み合わせた電極である。なお、図１（ｂ）において、
２の部分は固定床型三次元電極の活性酸素発生剤担持部
分であってもよい。図１（ｃ）は、電極全体が活性酸素
発生剤担持固定床型三次元電極２である態様を示す。図
１（ｄ）は、目詰まり防止を考慮し中央部に孔径の大き
い固定床型三次元電極３を配し、両側に活性酸素発生剤
担持固定床型三次元電極２を配した態様を示す。The fixed-bed type three-dimensional electrode of the present invention will be described with reference to FIG. FIG. 1 is a longitudinal sectional view of a fixed-bed type three-dimensional electrode. FIG. 1A shows a fixed-bed type three-dimensional electrode 1 made of carbon or metal. FIG. 1B shows an electrode obtained by combining a fixed bed type three-dimensional electrode 1 of carbonaceous or metal and a fixed bed type three-dimensional electrode 2 carrying an active oxygen generating agent. In FIG. 1B,
The portion 2 may be an active oxygen generating agent-supporting portion of the fixed bed type three-dimensional electrode. FIG. 1C shows an embodiment in which the entire electrode is a fixed-bed type three-dimensional electrode 2 carrying an active oxygen generating agent. FIG. 1D shows a mode in which a fixed-bed type three-dimensional electrode 3 having a large hole diameter is disposed at the center in consideration of clogging prevention, and an active oxygen generator-carrying fixed-bed type three-dimensional electrode 2 is disposed on both sides. .
【００４２】固定床型三次元電極に担持した活性酸素発
生剤は電圧を印加しなくても活性酸素を発生するため殺
菌に効果があるが、連続的な活性酸素発生のために電圧
を印加することが好ましい。The active oxygen generating agent supported on the fixed-bed type three-dimensional electrode generates active oxygen without applying a voltage, and is effective for sterilization. However, a voltage is applied for continuous active oxygen generation. Is preferred.
【００４３】固定床型三次元電極電解槽は、例えば、筒
状の電解槽容器内に複数個の固定床型三次元電極を収容
し、その上下に給電用電極を配置し、該給電用電極に電
圧を印加することによって、各々の固定床型三次元電極
を分極させる。ここに被処理水を通過させることによっ
て水を処理することができるのである。In the fixed-bed type three-dimensional electrode electrolytic cell, for example, a plurality of fixed-bed type three-dimensional electrodes are accommodated in a cylindrical electrolytic cell container, and power supply electrodes are arranged above and below the fixed-type three-dimensional electrode. By applying a voltage to each of the fixed-bed type three-dimensional electrodes. The water can be treated by passing the water to be treated here.
【００４４】電圧の印加法としては、積層した固定床型
三次元電極の端に設置した平板状又はエキスバンドメッ
シュ状やパーフォレーティッドプレート状等の多孔質体
等からなる給電用電極間に直流電圧あるいは周波数の低
い交流電圧を印加して前記固定床型三次元電極を分極さ
せ該固定床型三次元電極の一端及び他端にそれぞれ陽極
及び陰極を形成させることが好ましい。As a method of applying a voltage, a direct current is applied between power supply electrodes made of a porous material such as a flat plate, an ex-band mesh, a perforated plate, or the like, which is provided at an end of a stacked fixed-bed type three-dimensional electrode. It is preferable to apply a voltage or an alternating voltage having a low frequency to polarize the fixed-bed type three-dimensional electrode to form an anode and a cathode at one end and the other end of the fixed-bed type three-dimensional electrode, respectively.
【００４５】前記固定床型三次元電極として活性炭、グ
ラファイト、炭素繊維等の炭素系材料を使用する場合、
前記炭素質固定床型三次元電極が陽極側で酸化され、電
極自身が崩壊したり、炭酸ガスとして溶解し易くなる。
これを防止するために前記炭素質固定床型三次元電極の
陽分極する側に、チタン等の基材上に酸化イリジウム、
酸化ルテニウム等の白金族金属酸化物、あるいは白金を
被覆し通常不溶性金属電極として使用される多孔質材料
又は網状材料を保護電極として、接触状態で設置するこ
とが好ましい。When a carbon-based material such as activated carbon, graphite, or carbon fiber is used as the fixed-bed type three-dimensional electrode,
The carbonaceous fixed bed type three-dimensional electrode is oxidized on the anode side, and the electrode itself collapses or is easily dissolved as carbon dioxide gas.
To prevent this, iridium oxide on a substrate such as titanium, on the side of positive polarization of the carbonaceous fixed bed type three-dimensional electrode,
It is preferable that a platinum group metal oxide such as ruthenium oxide, or a porous material or a mesh material which is coated with platinum and which is usually used as an insoluble metal electrode, is provided in contact with a protective electrode.
【００４６】固定床型三次元電極電解槽に印加する電位
は、分極した陽極部分では、電極−微生物の反応が起こ
る、０．７Ｖ（ｖｓ．ＳＣＥ）以上、陰極部分では、活
性酸素の連続的な発生のために、活性酸素発生剤の還元
が起こる−０．１Ｖ（ｖｓ．ＳＣＥ）以下の電位が各電
極に印加されていることが好ましい。The potential applied to the fixed-bed type three-dimensional electrode electrolytic cell is 0.7 V (vs. SCE) or more at the polarized anode part where an electrode-microorganism reaction occurs. For this purpose, it is preferable that a potential of -0.1 V (vs. SCE) or less, at which reduction of the active oxygen generating agent occurs, is applied to each electrode.
【００４７】上述の電圧を、一定周期で極性が反転する
直流または、１０Ｈｚ以下の交流を印加することによ
り、電極表面への金属イオンの析出を防止、及び効果的
な殺菌も期待できる。By applying a direct current whose polarity is inverted at a constant cycle or an alternating current of 10 Hz or less to the above-mentioned voltage, it is possible to prevent the deposition of metal ions on the electrode surface and to expect effective sterilization.
【００４８】ただし、例えば電導度５μＳ／ｃｍ以下の
イオン交換水のような、電圧の印加による金属イオンの
析出の心配のない被処理水の場合、固定床型三次元電極
の陰極に分極する側にのみ活性酸素発生剤を担持させ、
活性酸素発生剤担持面を陰極に、担持していない面を陽
極に分極させ、電圧の反転を行わず、処理することも可
能であり、より効率的である。However, in the case of water to be treated, such as ion-exchanged water having an electric conductivity of 5 μS / cm or less, in which metal ions are not likely to be precipitated by applying a voltage, the side of the fixed-bed type three-dimensional electrode that is polarized to the cathode. Only active oxygen generator is supported on
It is possible to polarize the active oxygen generator-carrying surface on the cathode and the non-carrying surface on the anode, and perform the processing without inverting the voltage, which is more efficient.
【００４９】しかし、固定床型三次元電極の中央部分は
分極していないため、この部分に微生物が付着し、増殖
することが懸念されている。そこで、例えば厚さ１〜３
ｍｍ程度で孔径が１００μｍ以上の微生物の付着しにく
い電極を中央に配するように、その両面、または片面を
活性酸素発生剤を担持した厚さ１〜３ｍｍ程度の電極で
はさみ、１組の固定床型三次元電極とすることで、分極
しない固定床型三次元電極の中央部での微生物の繁殖を
防ぎ、より効率的な水処理を行うこともできる。However, since the central part of the fixed-bed type three-dimensional electrode is not polarized, there is a concern that microorganisms may adhere to this part and proliferate. Then, for example, thickness 1-3
In order to arrange at the center an electrode with a pore diameter of about 100 mm that is hard to adhere to microorganisms, both sides, or one side, are sandwiched by electrodes with a thickness of about 1 to 3 mm carrying an active oxygen generating agent, and one set is fixed. The use of the floor-type three-dimensional electrode prevents the growth of microorganisms in the central part of the non-polarized fixed-bed type three-dimensional electrode, thereby enabling more efficient water treatment.
【００５０】活性酸素発生剤による活性酸素の発生量は
被処理水中の溶存酸素濃度に依存する。すなわち、被処
理水中にある程度の酸素が溶存していることが必要であ
る。しかし、発生した活性酸素は直ちに過酸化水素に変
わってしまい、水中の溶存酸素濃度は過酸化水素濃度に
反比例して減少していく。一般に純水中の溶存酸素濃度
は１０ｐｐｍ以下である。そのため、密閉された容器内
での循環処理では、酸素をバブリングなどで補充しなけ
れば効果的な処理を行うことは難しい。The amount of active oxygen generated by the active oxygen generator depends on the concentration of dissolved oxygen in the water to be treated. That is, it is necessary that some oxygen is dissolved in the water to be treated. However, the generated active oxygen is immediately converted to hydrogen peroxide, and the dissolved oxygen concentration in the water decreases in inverse proportion to the hydrogen peroxide concentration. Generally, the concentration of dissolved oxygen in pure water is 10 ppm or less. Therefore, in the circulating process in a closed container, it is difficult to perform an effective process unless oxygen is supplemented by bubbling or the like.
【００５１】しかし、固定床型三次元電極の保護電極
に、例えば白金を用いたとき、活性酸素より生じた過酸
化水素が保護電極上で分解し、酸素を生成する。すなわ
ち、活性酸素発生剤により最終的に生成される過酸化水
素を再び酸素に戻すことによって、酸素添加の必要のな
い被処理水の処理が可能となる。従って、５０ｐｐｍ以
下の溶存酸素濃度の水であっても殺菌が可能となる。However, when, for example, platinum is used for the protective electrode of the fixed-bed type three-dimensional electrode, hydrogen peroxide generated from active oxygen is decomposed on the protective electrode to generate oxygen. That is, by returning the hydrogen peroxide finally generated by the active oxygen generating agent back to oxygen, it becomes possible to treat the water to be treated which does not require the addition of oxygen. Therefore, sterilization is possible even with water having a dissolved oxygen concentration of 50 ppm or less.
【００５２】同様に、過酸化水素を含有した水を固定床
型三次元電極電解槽に通水すると、保護電極として使用
している白金の触媒作用により過酸化水素が分解され、
溶存酸素濃度が上昇する。従って、溶存酸素の少ない被
処理水を処理する場合、被処理水に過酸化水素を添加す
ることで水中の溶存酸素濃度を増やし、更に効果的な殺
菌を行うことも可能である。添加する過酸化水素の量は
特に限定はされないが、添加後の最終濃度として１〜１
００ｐｐｍが好ましく、３〜３０ｐｐｍがより好まし
い。Similarly, when water containing hydrogen peroxide is passed through a fixed-bed type three-dimensional electrode electrolytic cell, hydrogen peroxide is decomposed by the catalytic action of platinum used as a protective electrode.
The dissolved oxygen concentration increases. Therefore, when treating the water to be treated with a small amount of dissolved oxygen, it is possible to increase the concentration of dissolved oxygen in the water by adding hydrogen peroxide to the water to be treated, and to perform more effective sterilization. The amount of hydrogen peroxide to be added is not particularly limited, but the final concentration after the addition is 1 to 1
00 ppm is preferable, and 3 to 30 ppm is more preferable.
【００５３】また、過酸化水素を添加できないような場
合、固定床型三次元電極に印加する電圧を固定床型三次
元電極の陽極に分極する部分が１．２Ｖ（ｖｓ．ＳＣ
Ｅ）以上の電位となるように設定することで、水の電気
分解が起こり、溶存酸素を増やすこともできる。When hydrogen peroxide cannot be added, the voltage applied to the fixed-bed type three-dimensional electrode is polarized to the anode of the fixed-bed type three-dimensional electrode at 1.2 V (vs. SC).
E) By setting the potential to be equal to or higher than the above, electrolysis of water occurs and dissolved oxygen can be increased.
【００５４】本発明では、電極への微生物の吸着、陽極
上での殺菌、陰極からの活性酸素による殺菌、陽極上で
の電気分解による酸素発生、さらに発生した過酸化水素
あるいは添加した過酸化水素の白金による酸素への分解
が多段に設置された固定床型三次元電極で同時に起こる
ことによって、殺菌効率を著しく向上させることができ
たと推測される。In the present invention, adsorption of microorganisms on the electrode, sterilization on the anode, sterilization with active oxygen from the cathode, generation of oxygen by electrolysis on the anode, generation of hydrogen peroxide or added hydrogen peroxide It is presumed that the decomposition of oxygen into oxygen by platinum simultaneously occurred in the fixed-bed type three-dimensional electrodes provided in multiple stages, thereby significantly improving the sterilization efficiency.
【００５５】[0055]
【実施例】次に本発明を実施例に基づき説明するが、本
発明の実施態様はこれに限定されない。Next, the present invention will be described based on examples, but embodiments of the present invention are not limited to these examples.
【００５６】実施例１ 固定床型三次元電極として、微細炭素粒子からなる厚さ
９ｍｍ、気孔率３０％，平均気孔径１５０μｍ、直径７
６ｍｍの多孔質グラファイト（東海カーボン株式会社
製：Ｇ−１００）を用いた。Example 1 A fixed bed type three-dimensional electrode was made of fine carbon particles, having a thickness of 9 mm, a porosity of 30%, an average pore diameter of 150 μm, and a diameter of 7
6 mm porous graphite (G-100 manufactured by Tokai Carbon Co., Ltd.) was used.
【００５７】活性酸素発生剤としてポリアニリンを用
い、上記多孔質グラファイトの片側にポリアニリンを電
解重合により図１（ｂ）に示すように担持させた。Polyaniline was used as an active oxygen generator, and polyaniline was supported on one side of the porous graphite by electrolytic polymerization as shown in FIG. 1 (b).
【００５８】上記の多孔質炭素電極を作用極、対極に白
金板、参照極に飽和甘コウ電極とし、アニリン０．１
Ｍ、硫酸０．５Ｍ、硫酸ナトリウム０．２Ｍ、ピリジン
０．３Ｍを含む水溶液に浸漬し、０．７Ｖ（ｖｓ．ＳＣ
Ｅ）４０分間電位を印加し、ポリアニリン担持多孔質グ
ラファイト電極を作製した。The above-described porous carbon electrode was used as a working electrode, a platinum plate was used as a counter electrode, a saturated sweet potato electrode was used as a reference electrode, and aniline 0.1 was used.
M, sulfuric acid 0.5M, sodium sulfate 0.2M, pyridine 0.3M and immersed in an aqueous solution containing 0.7V (vs. SC
E) A potential was applied for 40 minutes to produce a polyaniline-supported porous graphite electrode.
【００５９】白金で被覆されたチタンメッシュ（厚み１
ｍｍ）を保護電極として用い、上述のポリアニリン担持
多孔質グラファイト電極を２枚の保護電極でサンドイッ
チし、これを１ｍｍの間隔で円筒容器内に８組積層し、
さらに上下に給電用電極を配し、図２に示すような本発
明の固定床型三次元電極電解槽を作製した。Titanium mesh (thickness 1) coated with platinum
mm) as a protective electrode, the above-mentioned polyaniline-supported porous graphite electrode was sandwiched between two protective electrodes, and eight sets of these were laminated in a cylindrical container at intervals of 1 mm.
Further, the power supply electrodes were arranged on the upper and lower sides to prepare a fixed-bed type three-dimensional electrode electrolytic cell of the present invention as shown in FIG.
【００６０】Ｐｓｅｕｄｏｍｏｎａｓ ｄｉｍｉｎｕｔ
ａを液体培地（普通ブイヨン培地、栄研化学製）を用い
て１日間培養し、菌体を５０００ｒｐｍにて遠心分離し
た後、純水で洗浄し、再度遠心分離した。これを予め貯
めておいた純水（電気伝導度１μＳ／ｃｍ以下）に添加
し被処理水とした。Pseudomonas diminut
a was cultured in a liquid medium (normal broth medium, manufactured by Eiken Chemical Co., Ltd.) for 1 day, and the cells were centrifuged at 5000 rpm, washed with pure water, and centrifuged again. This was added to previously stored pure water (electrical conductivity: 1 μS / cm or less) to obtain treated water.
【００６１】これを本発明の電解槽及び比較の電解槽に
１．２ｋｇ／ｃｍ2の圧力で送水し、給電用電極端子に
直流３４Ｖを印加した。そして、運転前と運転開始後の
被処理水を経時的に採水し、これに含まれる生菌数を普
通寒天培地（栄研化学製）を用いた寒天平板法にて測定
した。This was supplied to the electrolytic cell of the present invention and the comparative electrolytic cell at a pressure of 1.2 kg / cm 2 , and a direct current of 34 V was applied to the power supply electrode terminal. Then, the water to be treated before and after operation was sampled with time, and the number of viable bacteria contained therein was measured by an agar plate method using an ordinary agar medium (manufactured by Eiken Chemical Co., Ltd.).
【００６２】比較として、担持量と同量のポリアニリン
を被処理水中に加える前と添加後の被処理水中の生菌数
を経時的に測定した。その結果を表１に示す。As a comparison, the number of viable bacteria in the water to be treated before and after the addition of the same amount of polyaniline to the water to be treated was measured over time. Table 1 shows the results.
【００６３】[0063]
【表１】 [Table 1]
【００６４】表１より、活性酸素発生剤であるポリアニ
リンを固定床型三次元電極に担持させることで、より効
果的な微生物の殺菌を行うことが可能であることが示さ
れた。Table 1 shows that by carrying polyaniline, which is an active oxygen generator, on a fixed-bed type three-dimensional electrode, more effective sterilization of microorganisms can be performed.
【００６５】実施例２ 実施例１と同様の多孔質グラファイトの全面にポリアニ
リンを担持した図１（ｃ）に示すような電極を作製し、
実施例１同様に円筒容器内に積層し、図３に示すような
本発明の電解槽を用意した。Example 2 An electrode as shown in FIG. 1 (c) was prepared, in which polyaniline was supported on the entire surface of the same porous graphite as in Example 1, and
As in Example 1, they were laminated in a cylindrical container to prepare an electrolytic cell of the present invention as shown in FIG.
【００６６】また、ポリアニリンを担持していない多孔
質グラファイト電極（図１（ａ））を詰めたものを比較
の電解槽とした（図４に示す）。A cell packed with a porous graphite electrode not carrying polyaniline (FIG. 1A) was used as a comparative electrolytic cell (FIG. 4).
【００６７】水道水（電気伝導度１５０μＳ／ｃｍ）に
Ｐｓｅｕｄｏｍｏｎａｓ ｄｉｍｉｎｕｔａを実施例１
同様に加え被処理水を調整し、本発明の電解槽及び比較
の電解槽に１．２ｋｇ／ｃｍ2の圧力で送水し、給電用
電極端子に直流３４Ｖを印加し、１分間隔で極性を反転
させ、電解槽通過前及び運転１時間後の水中の生菌数を
測定した。その結果を表２に示す。Example 1 Pseudomonas diminuta in tap water (electrical conductivity 150 μS / cm)
Similarly, the water to be treated was adjusted, water was supplied to the electrolytic cell of the present invention and the comparative electrolytic cell at a pressure of 1.2 kg / cm 2 , 34 V DC was applied to the power supply electrode terminal, and the polarity was changed at one minute intervals. After inversion, the number of viable bacteria in water before passing through the electrolytic cell and one hour after the operation was measured. Table 2 shows the results.
【００６８】[0068]
【表２】 [Table 2]
【００６９】表２から、ポリアニリン活性酸素発生剤を
担持していない電極より、制菌効果に優れていることが
判明した。From Table 2, it was found that the electrode having no polyaniline active oxygen generator had a better bacteriostatic effect.
【００７０】実施例３ 固定床型三次元電極として、微細炭素粒子からなる厚さ
３ｍｍ、気孔率３０％、平均気孔径１５０μｍ、直径７
６ｍｍの多孔質グラファイトを用いた。Example 3 A fixed bed type three-dimensional electrode was formed of fine carbon particles, having a thickness of 3 mm, a porosity of 30%, an average pore diameter of 150 μm, and a diameter of 7
6 mm porous graphite was used.
【００７１】活性酸素発生剤としてポリアニリンを上記
多孔質グラファイト上に実施例１同様の手法で担持させ
た。Polyaniline as an active oxygen generator was supported on the porous graphite in the same manner as in Example 1.
【００７２】微細炭素粒子からなる厚さ３ｍｍ、気孔率
１５％、平均気孔径５００μｍ、直径７６ｍｍの多孔質
グラファイトを中央に配し、上記のポリアニリン担持電
極で両側を挟み、１組の図１（ｄ）に示すような固定床
型三次元電極を作製した。A porous graphite having a thickness of 3 mm, a porosity of 15%, an average pore diameter of 500 μm and a diameter of 76 mm made of fine carbon particles was arranged at the center, and both sides were sandwiched by the above-mentioned polyaniline-supported electrode. A fixed bed type three-dimensional electrode as shown in d) was produced.
【００７３】白金で被覆されたチタンメッシュ（厚み１
ｍｍ）を保護電極として用い、上記固定床型三次元電極
をサンドイッチし、これを８組詰め図５で示す固定床型
三次元電極電解槽を作製した。Titanium mesh (thickness 1) coated with platinum
mm) as a protective electrode, the above fixed-bed type three-dimensional electrode was sandwiched, and eight sets of these were packed to produce a fixed-bed type three-dimensional electrode electrolytic cell shown in FIG.
【００７４】実施例２と同様の被処理水を本発明の電解
槽及び比較の電解槽に１．２ｋｇ／ｃｍ2の圧力で送水
し、給電用電極端子に直流３４Ｖを印加し、１分間隔で
極性を反転させた。電解槽通過前と運転後の被処理水を
採水し、これに含まれる生菌数及び、処理流量を経時的
に測定した。The same water to be treated as in Example 2 was supplied to the electrolytic cell of the present invention and the comparative electrolytic cell at a pressure of 1.2 kg / cm 2 , and a direct current of 34 V was applied to the power supply electrode terminal. To reverse the polarity. The water to be treated was sampled before passing through the electrolytic cell and after the operation, and the number of viable bacteria contained therein and the treatment flow rate were measured over time.
【００７５】比較として、微細炭素粒子からなる厚さ３
ｍｍ、気孔率１５％，平均気孔径５００μｍ、直径７６
ｍｍの多孔質グラファイトを中央に配し、その両側をポ
リアニリン担持なしの微細炭素粒子からなる厚さ３ｍ
ｍ、気孔率３０％、平均気孔径１５０μｍ、直径７６ｍ
ｍの多孔質グラファイトで挟んだ固定床三次元電極を詰
めた電解槽：比較（１）（図６に示す）及び、実施例２
の電解槽：比較（２）（図４に示す）で同様の試験を行
った。その結果を表３に示す。As a comparison, the thickness 3 of fine carbon particles
mm, porosity 15%, average pore diameter 500 μm, diameter 76
mm of porous graphite is disposed at the center, and both sides thereof are made of fine carbon particles without supporting polyaniline, and have a thickness of 3 m.
m, porosity 30%, average pore diameter 150μm, diameter 76m
Electrolyzer packed with a fixed-bed three-dimensional electrode sandwiched between m porous gels: Comparative (1) (shown in FIG. 6) and Example 2.
Electrolyzer: The same test was performed in Comparative (2) (shown in FIG. 4). Table 3 shows the results.
【００７６】[0076]
【表３】 [Table 3]
【００７７】表３から、活性酸素担持多孔質炭素電極の
中央にそれより気孔径の大きい電極を配することで、制
菌効果に優れて、かつより大量の被処理水の処理が可能
となることが確認された。From Table 3, it can be seen that by disposing an electrode having a larger pore diameter at the center of the active oxygen-carrying porous carbon electrode, it is possible to treat a larger amount of water to be treated with an excellent bacteriostatic effect. It was confirmed that.
【００７８】実施例４ 実施例１と同様の電解槽を用意した。過酸化水素濃度が
１０ｐｐｍとなるように添加した純水（溶存酸素濃度５
ｐｐｍ以下）にＰｓｅｕｄｏｍｏｎａｓ ｄｉｍｉｎｕ
ｔａを実施例１同様に加え、被処理水を調整し、１．２
ｋｇ／ｃｍ2の圧力で送水し、給電用電極端子に直流３
４Ｖを印加し、電解槽通過前及び運転後の生菌数を経時
的に測定した。Example 4 An electrolytic cell similar to that of Example 1 was prepared. Pure water added so that the hydrogen peroxide concentration becomes 10 ppm (dissolved oxygen concentration 5 ppm
ppm or less) to Pseudomonas diminu
ta was added in the same manner as in Example 1, and the water to be treated was adjusted.
Water is supplied at a pressure of kg / cm 2 , and a direct current of 3
4 V was applied, and the number of viable bacteria before passing through the electrolytic cell and after the operation was measured over time.
【００７９】比較として、溶存酸素濃度５ｐｐｍ以下の
純水に過酸化水素添加しないものを被処理水とし、同様
の電解槽に送水した。その結果を表４に示す。For comparison, pure water having a dissolved oxygen concentration of 5 ppm or less, to which no hydrogen peroxide was added, was treated as water to be treated, and sent to the same electrolytic cell. Table 4 shows the results.
【００８０】[0080]
【表４】 [Table 4]
【００８１】表４から、被処理水に過酸化水素の添加を
行うことで、溶存酸素濃度の低い被処理水でも酸素のバ
ブリングを行うことなく、効果的な殺菌が可能であるこ
とが明らかとなった。From Table 4, it is clear that by adding hydrogen peroxide to the water to be treated, it is possible to effectively sterilize the water to be treated having a low dissolved oxygen concentration without bubbling oxygen. became.
【００８２】[0082]
【発明の効果】本発明により、固定床型三次元電極に活
性酸素発生剤を担持させることにより、分極した陽極以
外の部分の有効な使用が可能となった。これらのことか
ら、固定床型三次元電極電解槽を用いる被処理水中の微
生物等を電気化学的に処理する方法において、殺菌効率
の向上が認められた。According to the present invention, by supporting an active oxygen generating agent on a fixed-bed type three-dimensional electrode, it is possible to effectively use parts other than the polarized anode. From these facts, it was confirmed that the method of electrochemically treating microorganisms and the like in the water to be treated using the fixed-bed type three-dimensional electrode electrolytic cell improved sterilization efficiency.
【図１】固定床型三次元電極を示す縦断面図である。FIG. 1 is a longitudinal sectional view showing a fixed-bed type three-dimensional electrode.
【図２】本発明の活性酸素発生剤を一面に担持した固定
床型三次元電極を用いた固定床型三次元電極電解槽の一
例を示す縦断面図である。FIG. 2 is a longitudinal sectional view showing an example of a fixed-bed type three-dimensional electrode electrolytic cell using a fixed-bed type three-dimensional electrode carrying the active oxygen generating agent of the present invention on one surface.
【図３】本発明の活性酸素発生剤を全体に担持した固定
床型三次元電極を用いた固定床型三次元電極電解槽の一
例を示す縦断面図である。FIG. 3 is a longitudinal sectional view showing an example of a fixed-bed type three-dimensional electrode electrolytic cell using a fixed-bed type three-dimensional electrode carrying the active oxygen generating agent of the present invention as a whole.
【図４】比較の固定床型三次元電極電解槽の縦断面図で
ある。FIG. 4 is a longitudinal sectional view of a comparative fixed-bed type three-dimensional electrode electrolytic cell.
【図５】本発明の孔径の大きい多孔質グラファイトを中
央に配し、活性酸素発生剤担持電極で両側を挟んだ固定
床型三次元電極を用いた固定床型三次元電極電解槽の一
例を示す縦断面図である。FIG. 5 shows an example of a fixed-bed type three-dimensional electrode electrolytic cell using a fixed-bed type three-dimensional electrode in which a porous graphite having a large pore diameter according to the present invention is disposed at the center and both sides are sandwiched by active oxygen generating agent-carrying electrodes. FIG.
【図６】比較の孔径の大きい多孔質グラファイトを中央
に配し、孔径の小さい多孔質グラファイトで両側を挟ん
だ活性酸素発生剤担持固定床型三次元電極を用いた固定
床型三次元電極電解槽の一例を示す縦断面図である。FIG. 6: Fixed-bed type three-dimensional electrode electrolysis using an active oxygen generating agent-carrying fixed-bed type three-dimensional electrode in which a comparatively large porous graphite is disposed at the center and both sides are sandwiched by porous graphite having a small pore diameter. It is a longitudinal section showing an example of a tank.
１ 固定床型三次元電極 ２ 活性酸素発生剤担持固定床型三次元電極 ３ 孔径の大きい固定床型三次元電極 ４ 補助電極 ５ Ｏ−リング ６ 円筒容器 ７ 給電用電極 ８ 電極ターミナル（外部から電力供給用） DESCRIPTION OF SYMBOLS 1 Fixed-bed type three-dimensional electrode 2 Fixed-bed type three-dimensional electrode carrying an active oxygen generating agent 3 Fixed-bed type three-dimensional electrode having a large pore size 4 Auxiliary electrode 5 O-ring 6 Cylindrical container 7 Power supply electrode 8 Electrode terminal (power from outside For supply)
Claims (16)
型三次元電極電解槽に用いられる固定床型三次元電極
が、活性酸素発生剤を担持することを特徴とする固定床
型三次元電極。1. A fixed bed type three-dimensional electrode, wherein a fixed bed type three-dimensional electrode used in a fixed bed type three-dimensional electrode electrolytic cell for electrochemically treating water to be treated carries an active oxygen generating agent. Original electrode.
次元電極の材質がグラファイト、グラッシーカーボン、
活性炭素等の炭素系材料又は金属であることを特徴とす
る請求項１記載の固定床型三次元電極。2. A fixed bed type three-dimensional electrode for supporting an active oxygen generating agent is made of graphite, glassy carbon,
The fixed-bed type three-dimensional electrode according to claim 1, wherein the electrode is a carbon-based material such as activated carbon or a metal.
極を少なくとも一つ有することを特徴とする固定床型三
次元電極電解槽。3. A fixed-bed type three-dimensional electrode electrolytic cell comprising at least one fixed-bed type three-dimensional electrode according to claim 1.
求項１又は２記載の固定床型三次元電極の陽極部分に、
０．７Ｖ（ｖｓ．ＳＣＥ）以上の電位を印加することを
特徴とする固定床型三次元電極電解槽。4. A fixed bed type three-dimensional electrode electrolytic cell, wherein the anode part of the fixed bed type three-dimensional electrode according to claim 1 or 2,
A fixed-bed type three-dimensional electrode electrolytic cell to which a potential of 0.7 V (vs. SCE) or more is applied.
求項１又は２記載の固定床型三次元電極の陰極部分に、
−０．１Ｖ（ｖｓ．ＳＣＥ）以下の電位を印加すること
を特徴とする固定床型三次元電極電解槽。5. A fixed bed type three-dimensional electrode electrolytic cell, wherein a cathode portion of the fixed bed type three-dimensional electrode according to claim 1 or 2 is:
A fixed-bed type three-dimensional electrode electrolytic cell to which a potential of -0.1 V (vs. SCE) or less is applied.
加する電圧の正負を一定時間毎に反転することを特徴と
する請求項３〜５のいずれか１項記載の固定床型三次元
電極電解槽。6. The fixed-bed type three-dimensional electrode according to claim 3, wherein in the fixed-bed type three-dimensional electrode electrolytic cell, the polarity of the applied voltage is reversed at regular time intervals. Electrolyzer.
床型三次元電極電解槽を用いることを特徴とする水処理
方法。7. A water treatment method using the fixed-bed type three-dimensional electrode electrolytic cell according to claim 3. Description:
特徴とする請求項７記載の水処理方法。8. The water treatment method according to claim 7, wherein hydrogen peroxide is added to the water to be treated.
性酸素発生剤を担持させることを特徴とする固定床型三
次元電極。9. A fixed bed type three-dimensional electrode characterized in that an active oxygen generating agent is supported on a side of the fixed bed type three-dimensional electrode which serves as a cathode.
三次元電極の材質が炭素質又は金属からなることを特徴
とする請求項９記載の固定床型三次元電極。10. The fixed-bed type three-dimensional electrode according to claim 9, wherein the material of the fixed-bed type three-dimensional electrode supporting an active oxygen generating agent is made of carbonaceous or metal.
元電極を少なくとも一つ有することを特徴とする固定床
型三次元電極電解槽。11. A fixed-bed type three-dimensional electrode electrolytic cell comprising at least one fixed-bed type three-dimensional electrode according to claim 9.
請求項９又は１０記載の固定床型三次元電極の陽極部分
に、０．７Ｖ（ｖｓ．ＳＣＥ）以上の電位を印加するこ
とを特徴とする固定床型三次元電極電解槽。12. A fixed bed type three-dimensional electrode electrolytic cell,
A fixed-bed three-dimensional electrode electrolytic cell, wherein a potential of 0.7 V (vs. SCE) or more is applied to an anode portion of the fixed-bed three-dimensional electrode according to claim 9.
請求項９又は１０記載の固定床型三次元電極の陰極部分
に、−０．１Ｖ（ｖｓ．ＳＣＥ）以下の電位を印加する
ことを特徴とする固定床型三次元電極電解槽。13. A fixed bed type three-dimensional electrode electrolytic cell,
A fixed-bed three-dimensional electrode electrolytic cell, wherein a potential of -0.1 V (vs. SCE) or less is applied to a cathode portion of the fixed-bed three-dimensional electrode according to claim 9.
印加する電圧の正負を反転しないことを特徴とする請求
項１１〜１３のいずれか１項記載の固定床型三次元電極
電解槽。14. In a fixed-bed type three-dimensional electrode electrolytic cell,
The fixed-bed three-dimensional electrode electrolytic cell according to any one of claims 11 to 13, wherein the polarity of the applied voltage is not inverted.
の固定床型三次元電極電解槽を用いることを特徴とする
水処理方法。15. A water treatment method comprising using the fixed-bed type three-dimensional electrode electrolytic cell according to claim 11. Description:
イオン交換水であることを特徴とする請求項１５記載の
水処理方法。16. The water treatment method according to claim 15, wherein the water to be treated is ion-exchanged water having an electric conductivity of 5 μS / cm or less.
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| CN1303257C (en) * | 2004-12-28 | 2007-03-07 | 中山大学 | Particle electrode catalyst filling for three-dimensional electrode and preparation method thereof |
| CN102001737A (en) * | 2010-10-26 | 2011-04-06 | 中山大学 | Electrocatalysis particle for treating cyanide-containing waste water and method for treating cyanide-containing waste water |
| JP2011098312A (en) * | 2009-11-09 | 2011-05-19 | Kuraray Co Ltd | Ion adsorption device and method of removing ionic substance |
| JP2012127617A (en) * | 2010-12-17 | 2012-07-05 | Mitsubishi Electric Corp | Water heater |
| CN105174596A (en) * | 2015-05-18 | 2015-12-23 | 南京万德斯环保科技有限公司 | Efficient and economical organic poisonous wastewater treatment method |
| CN110713235A (en) * | 2019-11-20 | 2020-01-21 | 北京林业大学 | Nickel-based complex-breaking catalytic composite particle electrode and preparation method thereof |
| CN112940249A (en) * | 2021-01-28 | 2021-06-11 | 暨南大学 | Method for synthesizing three-dimensional electrode homogeneous polypyrrole nanowire array based on internal filtering flow |
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1998
- 1998-03-27 JP JP8130298A patent/JPH11277064A/en active Pending
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| CN1303257C (en) * | 2004-12-28 | 2007-03-07 | 中山大学 | Particle electrode catalyst filling for three-dimensional electrode and preparation method thereof |
| JP2011098312A (en) * | 2009-11-09 | 2011-05-19 | Kuraray Co Ltd | Ion adsorption device and method of removing ionic substance |
| CN102001737A (en) * | 2010-10-26 | 2011-04-06 | 中山大学 | Electrocatalysis particle for treating cyanide-containing waste water and method for treating cyanide-containing waste water |
| JP2012127617A (en) * | 2010-12-17 | 2012-07-05 | Mitsubishi Electric Corp | Water heater |
| CN105174596A (en) * | 2015-05-18 | 2015-12-23 | 南京万德斯环保科技有限公司 | Efficient and economical organic poisonous wastewater treatment method |
| CN110713235A (en) * | 2019-11-20 | 2020-01-21 | 北京林业大学 | Nickel-based complex-breaking catalytic composite particle electrode and preparation method thereof |
| CN112940249A (en) * | 2021-01-28 | 2021-06-11 | 暨南大学 | Method for synthesizing three-dimensional electrode homogeneous polypyrrole nanowire array based on internal filtering flow |
| CN112940249B (en) * | 2021-01-28 | 2023-04-07 | 暨南大学 | Method for synthesizing three-dimensional electrode homogeneous polypyrrole nanowire array based on internal filtering flow |
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