JP3020551B2 - Electrochemical treatment of treated water containing microorganisms - Google Patents

Description

【発明の詳細な説明】 （産業上の利用分野） 本発明は、微生物を含有する35℃以上の被処理水の各
種性能劣化を抑制するために前記被処理水を電気化学的
に処理するための方法に関し、より詳細には特に微生物
繁殖に好適な35℃の被処理水特に浴場水を固定床型三次
元電極電解槽を使用して電気化学的に処理することによ
り前記被処理水中の微生物の滅菌を効果的に行うための
方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial application field) The present invention is to electrochemically treat the water to be treated in order to suppress various performance deteriorations of the water to be treated containing microorganisms at 35 ° C. or higher. More specifically, the microorganisms in the water to be treated are electrochemically treated using a fixed-bed type three-dimensional electrode electrolytic cell, particularly the water to be treated at 35 ° C., which is particularly suitable for the propagation of microorganisms. The present invention relates to a method for effectively performing sterilization.

（従来技術） 従来から各種用途に多種類の水溶液や他の物質を溶解
していない単独の水が使用されている。これらの水溶液
等は溶質が適度な養分を提供し、あるいは該水溶液の液
温が繁殖に好ましい比較的高温度であると、細菌等の微
生物が繁殖して該微生物は前記水溶液等の性能劣化を起
こしたり処理装置内に浮遊したり蓄積して処理装置の機
能を損なうことが多い。(Prior Art) Conventionally, various types of aqueous solutions and single water in which other substances are not dissolved have been used for various applications. In these aqueous solutions and the like, when the solute provides an appropriate nutrient, or when the temperature of the aqueous solution is a relatively high temperature suitable for propagation, microorganisms such as bacteria propagate and the microorganisms deteriorate the performance of the aqueous solution or the like. Often, they rise or float or accumulate in the processing apparatus, impairing the function of the processing apparatus.

例えば近年の家庭用浴槽の普及や温泉ブームから浴場
水の使用量が増大しているが、該浴場水は40℃前後の微
生物が最も繁殖し易い液温を有するため、入浴に使用せ
ずに単に放置しておくだけでも微生物が急速に繁殖して
汚染され、使用を継続出来なくなり、入浴を繰り返すと
人体の垢等が浮遊してこの傾向はより顕著になる。繁殖
した微生物は微小であるため濾過操作では除去しにく
く、特に銭湯などではその使用量が膨大であるため、汚
染された浴場水の再生を簡単な処理操作で行うことが出
来れば大幅なコストダウンが可能になる。For example, the use of bath water has increased due to the spread of household bath tubs and the hot spring boom in recent years, but since the bath water has a liquid temperature of around 40 ° C. where microorganisms are most likely to propagate, it is not used for bathing. Even if it is simply left alone, the microorganisms will rapidly grow and become contaminated, making it impossible to continue using it. If bathing is repeated, dirt and the like of the human body will float and this tendency will become more remarkable. Propagating microorganisms are so small that they are difficult to remove by filtration, and in public baths, etc., the amount of use is enormous. Becomes possible.

（発明が解決しようとする問題点） 前述した通り、従来の浴場水等の滅菌処理では十分な
滅菌効果を得ることが出来ず、より簡便かつ安価に多く
の微生物を含有する被処理水の滅菌処理を可能にする方
法の出現が望まれている。(Problems to be Solved by the Invention) As described above, a conventional sterilization treatment of bath water cannot provide a sufficient sterilization effect, and sterilization of water to be treated containing many microorganisms more easily and inexpensively. The advent of methods that allow processing is desired.

（発明の目的） 本発明は、前述の従来技術の欠点を解消し、多くの被
処理水を含有する高温の被処理水を電気化学的に滅菌す
る方法を提供することを目的とする。(Object of the Invention) An object of the present invention is to solve the above-mentioned drawbacks of the prior art and to provide a method for electrochemically sterilizing high-temperature treated water containing a large amount of treated water.

（問題点を解決するための手段） 本発明は、微生物を含む被処理水を固定床型三次元電
極電解槽に供給し、前記被処理水中の微生物を多孔質か
つブロック状の前記電極に接触させ死滅させて該被処理
水を電気化学的に処理することを特徴とする被処理水の
処理方法。なお本発明では電極表面上で実質的な酸化還
元反応のような電気化学反応を生起していないことがあ
るので本発明方法に使用される槽は電気化学的処理装置
というべきであるが、一般呼称に従って電解槽と称す
る。(Means for Solving the Problems) The present invention supplies treated water containing microorganisms to a fixed-bed type three-dimensional electrode electrolytic cell, and brings the microorganisms in the treated water into contact with the porous and block-shaped electrode. And treating the water to be treated electrochemically. In the present invention, since the electrochemical reaction such as a substantial oxidation-reduction reaction may not occur on the electrode surface, the tank used in the method of the present invention should be called an electrochemical treatment apparatus. It is called an electrolytic cell according to its name.

以下本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.

本発明は、好ましくは35℃以上の被処理水例えば浴場
水を固定床型三次元電極電解槽に供給し該電解槽に直流
又は交流電圧を印加し前記写真処理液等の被処理水中の
微生物の滅菌を行うことを特徴とするものである。本発
明の微生物には、細菌（バクテリア）、糸状菌（黴）、
酵母、変形菌、単細胞の藻類、原生動物、ウイルス等が
含まれる。The present invention preferably provides microorganisms in the water to be treated, such as the photographic processing solution, by supplying treated water having a temperature of 35 ° C. or higher, such as bath water, to a fixed-bed type three-dimensional electrode electrolytic cell and applying a DC or AC voltage to the electrolytic cell. Is characterized by performing sterilization. The microorganism of the present invention includes bacteria (bacteria), filamentous fungi (molds),
Includes yeast, deformed fungi, unicellular algae, protozoa, viruses and the like.

前記被処理水例えば家庭用浴槽や銭湯で使用される浴
場水は最も微生物の繁殖に適した35〜45℃の温度に維持
されるため僅少量の微生物が短時間で莫大な数に繁殖す
る。The water to be treated, for example, bath water used in a home tub or a public bath, is maintained at a temperature of 35 to 45 ° C., which is most suitable for the propagation of microorganisms.

該被処理水を固定床型三次元電極電解層に供給する
と、該被処理水中の微生物は液流動によって前記電解槽
の陽極や陰極あるいは後述する誘電体や固定床形成用粒
子等に接触しそれらの表面で強力な酸化還元反応を受け
たり高電位の電流に接触し、その活動が弱まったり自身
が死滅して滅菌が行われると考えられる。When the water to be treated is supplied to the fixed bed type three-dimensional electrode electrolytic layer, the microorganisms in the water to be treated come into contact with an anode or a cathode of the electrolytic cell or a dielectric or fixed bed forming particles to be described later by liquid flow. It is thought that a strong redox reaction or contact with a high-potential electric current occurs on the surface of the surface, and its activity is weakened or the body itself is killed and sterilization is performed.

従って本発明方法では、被処理水中の微生物が電圧が
印加された電極や誘電体や固定床形成用粒子等に接触す
れば十分であり、両極間に電流を流して水素及び酸素等
のガス発生を伴う実質的な電解反応を生起させることは
必須ではなく、むしろ実質的な電解反応が生じない低い
電位を電極表面に印加することが好ましい。これは微生
物を滅菌する以外のガス発生反応に無駄な電力を使うこ
とになり不経済だからであり、又それら発生ガスが電極
表面上を覆ってしまい微生物が電極表面と接触する効率
も低下させ滅菌効率を悪くする。Therefore, in the method of the present invention, it is sufficient that the microorganisms in the water to be treated come into contact with the electrode, the dielectric, the particles for forming the fixed bed, etc., to which a voltage is applied. It is not essential to cause a substantial electrolytic reaction accompanied by the above, but rather it is preferable to apply a low potential at which no substantial electrolytic reaction occurs to the electrode surface. This is because wasteful electric power is used for gas generation reactions other than the sterilization of microorganisms, which is uneconomical.In addition, the generated gas covers the surface of the electrode and the efficiency with which microorganisms come into contact with the electrode surface is reduced, resulting in sterilization. Inefficient.

従って本発明においては、印加電位を陽極電位が実質
的な酸素発生を伴わない＋0.2〜＋1.2V（vs.SCE）、陰
極電位が実質的に水素発生を伴わない０〜ー1.0V（vs.S
CE）となるようにすることが望ましいが、発生ガスによ
り液組成に変化が生じてもさほど問題にならないため、
陽極電位を＋2.0V（vs.SHE）より卑な電位とし、陰極電
位がー2.0V（vs.SHE）より貴な電位とすることも出来
る。Therefore, in the present invention, the applied potential is +0.2 to +1.2 V (vs. SCE) where the anode potential does not substantially involve oxygen generation, and 0 to −1.0 V (the cathode potential does not substantially involve hydrogen evolution). vs. S
CE) is desirable, but it does not matter much if the liquid composition changes due to the generated gas.
The anode potential can be set to a potential lower than +2.0 V (vs. SHE), and the cathode potential can be set to a potential nobler than -2.0 V (vs. SHE).

しかし浴場水等の大量処理の必要がある被処理水の場
合には、本発明方法による滅菌処理に必要な電力量は処
理コストの大部分を占めることが多い。電力量は、〔電
力〕＝〔電圧〕×〔電流〕で表され、電流が流れずガス
が発生しない場合には電力量は零であるが、ガス発生が
生ずる程度の電流が流れると処理すべき水量が莫大であ
るため消費電力量も莫大になる。従って消費電力量を極
力少なくするためには更に電圧値を減少させなければな
らない。処理すべき水量が僅かで流れる電流も僅かな場
合は電圧値の増減はさほど消費電力量には影響しない
が、本発明のように例えば浴場水のような大量処理の場
合には僅かな電圧降下が大きく消費電力量を減少させ
る。通常の電解槽における電解電圧は、〔陽極ターミナ
ルと陽極間の抵抗による電圧降下〕＋〔陽極の理論電解
電圧〕＋〔陽極の過電圧〕＋〔溶液抵抗による電圧降
下〕＋〔陰極の理論電解電圧〕＋〔陰極の過電圧〕＋
〔陰極ターミナルと陰極間の抵抗による電圧降下〕によ
り表される。これらのうち理論電解電圧と過電圧は電解
反応の種類を変えるか、電極の材質や電流密度を変えな
ければ変化することがなく、ターミナルと電極間の抵抗
も導線を太くするといったことで減少させることができ
るが有効な方法ではなく、電解電圧を減少させるために
は溶液抵抗を小さくすることがその効率が非常に大きく
最も望ましい。溶液抵抗を減少させる手段としては、溶
液の導電率を上昇させる、両電極間の距離を小さくする
といった方法があるが、浴場水等に例えば食塩や硫酸ナ
トリウム等を添加して導電率を上昇させることは現実的
ではない。従って両電極間の電極間距離を小さくして溶
液抵抗を小さくすることが好ましいが、本発明のごとく
固定床型の三次元電極を使用する場合には両電極間の極
間距離を小さくして溶液抵抗を小さくするにも限界があ
り、両電極が接触しない最低間隔距離は0.1mmである。
従って本発明の電気化学的処理においては好ましくは実
際に効率良く処理が行われていることを確認するために
最小限の電流を流し、僅少量のガスを発生させながら電
解処理することが望ましい。However, in the case of water to be treated, such as bath water, which needs to be treated in large amounts, the amount of power required for the sterilization treatment by the method of the present invention often accounts for a large part of the treatment cost. The amount of power is represented by [power] = [voltage] × [current]. When no current flows and no gas is generated, the power amount is zero, but processing is performed when a current sufficient to generate gas flows. Since the amount of water to be consumed is enormous, the amount of power consumption also becomes enormous. Therefore, in order to minimize the power consumption, the voltage value must be further reduced. When the amount of water to be treated is small and the flowing current is also small, the increase or decrease of the voltage value does not significantly affect the power consumption. However, in the case of a large amount treatment such as bath water as in the present invention, a small voltage drop occurs. Greatly reduces power consumption. The electrolysis voltage in a normal electrolytic cell is [voltage drop due to the resistance between the anode terminal and the anode] + [theoretical electrolysis voltage at the anode] + [overvoltage at the anode] + [voltage drop due to the solution resistance] + [theoretical electrolysis voltage at the cathode] ] + [Cathode overvoltage] +
[Voltage drop due to resistance between cathode terminal and cathode]. Of these, the theoretical electrolysis voltage and overvoltage do not change unless the type of electrolysis reaction is changed or the material and current density of the electrode are changed, and the resistance between the terminal and the electrode must be reduced by making the conductor thicker. However, this is not an effective method, and in order to reduce the electrolysis voltage, it is most desirable to reduce the solution resistance because the efficiency is very large. Means for reducing the solution resistance include increasing the conductivity of the solution and reducing the distance between the two electrodes, but increasing the conductivity by adding, for example, salt or sodium sulfate to bath water or the like. That is not realistic. Therefore, it is preferable to reduce the solution resistance by reducing the electrode distance between the two electrodes, but when using a fixed-bed type three-dimensional electrode as in the present invention, the electrode distance between the two electrodes is reduced. There is also a limit in reducing the solution resistance, and the minimum distance between the two electrodes where they do not contact is 0.1 mm.
Therefore, in the electrochemical treatment of the present invention, it is preferable to conduct the electrolytic treatment while supplying a minimum current and generating a small amount of gas in order to confirm that the treatment is actually being performed efficiently.

浴場水のような大量処理の場合にガス発生が伴うと、
発生するガスつまり酸素ガスと水素ガスは通常爆発限界
内の混合比で発生し、爆発の危険を回避するために空気
等の不活性ガスで希釈することが望ましく、例えば電解
槽出口に発生する電解ガスの分離手段と分離後の該電解
ガスを空気で希釈して電解ガス濃度が４容量％以下にな
るよう希釈する手段を設置することができる。When gas generation accompanies large-scale treatment such as bath water,
The generated gases, that is, oxygen gas and hydrogen gas, are usually generated at a mixing ratio within the explosion limit, and it is desirable to dilute with an inert gas such as air to avoid the danger of explosion. A gas separating means and a means for diluting the separated electrolytic gas with air so that the electrolytic gas concentration becomes 4% by volume or less can be provided.

大量処理が必要な被処理水の処理用に使用する電解槽
は、複極型固定床式三次元電極電解槽とすることが好ま
しい。これらの被処理水の場合、処理すべき水量は莫大
で例えば１時間当たり数トンとなるため、電解槽単位体
積当たりの処理能力の高い電解槽である複極型固定床式
電解槽の使用が望ましく、該電解槽の使用により処理す
べき被処理水との接触面積を増大させることができ、こ
れにより装置サイズを小さくし、かつ電解の効率を上げ
ることができる点で有利である。It is preferable that the electrolytic cell used for the treatment of the water to be treated which requires a large amount of treatment is a bipolar fixed-bed three-dimensional electrode electrolytic cell. In the case of these waters to be treated, since the amount of water to be treated is enormous, for example, several tons per hour, it is necessary to use a bipolar fixed-bed type electrolytic cell having a high treating capacity per unit volume of the electrolytic cell. Desirably, the use of the electrolytic cell can increase the contact area with the water to be treated, which is advantageous in that the size of the apparatus can be reduced and the efficiency of electrolysis can be increased.

更に水道水には前述の微生物以外にカルシウムイオン
やマグネシウムイオンが含有され水道水の配管の内壁へ
のこれらのイオンの水酸化物としての析出による配管の
閉塞は大きな問題となっているが、多くの場合水道水を
水源として使用する浴場水等にもカルシウムイオンやマ
グネシウムイオンが含有され、該イオンは配管に付着し
たりする。被処理水中の前記カルシウムイオン及びマグ
ネシウムイオンは、該被処理水を固定床型三次元電極電
解槽を使用して電気化学的に処理すると該電解槽の陰極
や三次元電極上でそれらの水酸化物として該陰極上等に
析出し除去される。Furthermore, tap water contains calcium ions and magnesium ions in addition to the above-mentioned microorganisms, and blockage of the pipe due to precipitation of these ions as hydroxide on the inner wall of the pipe of the tap water is a major problem, In this case, calcium ions and magnesium ions are also contained in bath water or the like using tap water as a water source, and the ions may adhere to piping. When the water to be treated is electrochemically treated using a fixed-bed type three-dimensional electrode electrolytic cell, the calcium ions and the magnesium ions in the water to be treated are hydroxylated on the cathode and the three-dimensional electrode of the electrolytic cell. The substance is deposited on the cathode and the like and removed.

本発明方法に使用する電解槽は、固定床型三次元電極
電解槽つまり固定床型単極式電解槽及び固定床式複極式
電解槽であり、これらの電解槽では該電解槽の三次元電
極が莫大な表面積を有するため電極表面と浴場水等の被
処理水との接触面積を増大させることが出来、これによ
り装置サイズを小さくし、かつ電気化学的処理の効率を
上げることができる点で有利である。The electrolytic cell used in the method of the present invention is a fixed-bed type three-dimensional electrode electrolytic cell, i.e., a fixed-bed type monopolar electrolytic cell and a fixed-bed bipolar electrode electrolytic cell. Since the electrode has an enormous surface area, the contact area between the electrode surface and the water to be treated such as bath water can be increased, thereby reducing the size of the apparatus and increasing the efficiency of the electrochemical treatment. Is advantageous.

本発明の固定床型三次元電極電解槽における電極は一
般に三次元電極と給電用電極を含み、該三次元電極は前
述の使用する電解槽に応じた形状を有し、固定床型複極
式電解槽を使用する場合には、前記被処理水が透過可能
な多孔質材料、つまり多孔質ブロック状の形状を有する
活性炭、グラファイト、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
のコーティングを施した材料から形成された複数個の多
孔質ブロック状の誘電体を直流電場内に置き、両端に設
置した平板状又はエキスパ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板体から成る給電用電極
間に直流電圧あるいは交流電圧を印加して前記誘電体を
分極させ該誘電体の一端及び他端にそれぞれ陽極及び陰
極を形成させて成る三次元電極を収容した固定床型複極
式電解槽とすることが可能であり、この他に単独で陽極
としてあるいは陰極として機能する三次元材料を交互に
短絡しないように設置しかつ電気的に接続して固定床型
複極式電解槽とすることができる。The electrodes in the fixed-bed type three-dimensional electrode electrolytic cell of the present invention generally include a three-dimensional electrode and a power supply electrode, and the three-dimensional electrode has a shape corresponding to the electrolytic cell used above, and is a fixed-bed type bipolar electrode. When using an electrolytic cell, a porous material through which the water to be treated is permeable, that is, activated carbon having a porous block shape, graphite, carbon-based material such as carbon fiber,
Or nickel, copper, stainless steel having the same shape,
Place a plurality of porous block-shaped dielectrics made of metal materials such as iron and titanium, and a material coated with a noble metal on those metal materials in a DC electric field, and place them in a flat plate or expanded mesh at both ends. A DC voltage or an AC voltage is applied between power supply electrodes formed of a perforated plate or a perforated plate to polarize the dielectric and form an anode and a cathode at one end and the other end of the dielectric, respectively. It is possible to use a fixed-bed type bipolar electrolytic cell containing three-dimensional electrodes consisting of three-dimensional electrodes. To form a fixed-bed bipolar battery.

前記誘電体として活性炭、グラファイト、炭素繊維等
の炭素系材料を使用しかつ陽極から酸素ガスを発生させ
ながら被処理水を処理する場合には、前記誘電体が酸素
ガスにより酸化され炭酸ガスとして溶解し易くなる。こ
れを防止するためには前記誘電体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
される多孔質材料を接触状態で設置し、酸素発生が主と
して該多孔質材料上で生ずるようにすればよい。When a carbon-based material such as activated carbon, graphite, or carbon fiber is used as the dielectric and water to be treated is treated while generating oxygen gas from the anode, the dielectric is oxidized by oxygen gas and dissolved as carbon dioxide. Easier to do. In order to prevent this, a porous material which is usually used as an insoluble metal electrode by coating a platinum group metal oxide such as iridium oxide or ruthenium oxide on a base material such as titanium on the side where the dielectric material is positively polarized is used. What is necessary is just to install in a contact state, and to generate | occur | produce oxygen mainly on this porous material.

又他のタイプの固定床型複極式電解槽として、例えば
円筒状の電解槽本体内に給電陽極及び陰極を設置し、該
給電用両極間に、三次元電極として機能する多数の導電
性固定床形成用粒子と該固定床形成用粒子より少数の電
気絶縁性の合成樹脂等から成る絶縁粒子とをほぼ均一に
混在させた電解槽がある。該電解槽では両給電用電極間
に通電して電位を印加すると、固定床形成用粒子が前記
誘電体と同様に分極しその一端が正に又他端が負に帯電
して各固定床形成用粒子に電位が生じ、各粒子に被処理
水中の微生物を滅菌する機能が付与される。なお前記絶
縁粒子は、前記両給電用電極が導電性の前記固定床形成
粒子により電気的に接続されて短絡することを防止する
機能を有する。In addition, as another type of fixed-bed type bipolar electrolytic cell, for example, a power supply anode and a cathode are installed in a cylindrical electrolytic cell body, and a large number of conductive fixing members functioning as three-dimensional electrodes are provided between the power supply electrodes. There is an electrolytic cell in which particles for forming a floor and insulating particles composed of an electrically insulating synthetic resin or the like having a smaller number than the particles for forming a fixed bed are almost uniformly mixed. In the electrolytic cell, when a potential is applied by applying a current between both power supply electrodes, the fixed bed forming particles are polarized in the same manner as the dielectric, and one end thereof is positively charged and the other end is negatively charged, thereby forming each fixed bed. A potential is generated in the particles for use, and a function of sterilizing microorganisms in the water to be treated is imparted to each particle. Note that the insulating particles have a function of preventing the two power supply electrodes from being electrically connected by the conductive fixed bed forming particles to cause a short circuit.

又単極式固定床型電解槽を使用する場合には、前記し
た誘電体又は単独で陽極としてあるいは陰極として機能
する三次元材料各１個を隔膜に介してあるいは介さずに
電解槽内に設置するようにする。When a monopolar fixed-bed type electrolytic cell is used, the above-described dielectric or one of three-dimensional materials that independently function as an anode or a cathode is installed in the electrolytic cell with or without a diaphragm. To do it.

いずれの形態の電極を使用する場合でも、処理すべき
被処理水が流れる電解槽内に液が電極や誘電体や微粒子
に接触せずに流通できる空隙があると被処理水の処理効
率が低下するため、電極等は電解槽内の被処理水の流れ
がショートパスしないように配置することが望ましい。Regardless of which type of electrode is used, the efficiency of the water to be treated decreases if there is a gap in the electrolytic cell through which the water to be treated flows without allowing the liquid to come into contact with the electrode, dielectric or fine particles. Therefore, it is desirable to arrange the electrodes and the like so that the flow of the water to be treated in the electrolytic cell does not short-pass.

前記電解槽に供給される被処理水の流量は、該被処理
水が効率的に電極等の表面と接触できるように規定すれ
ばよく、完全な層流であると横方向の移動が少なく電
極、誘電体及び微粒子表面との接触が少なくなるため、
乱流状態を形成するようにすることが好ましく、500以
上のレイノルズ数を有する乱流とすることが特に好まし
い。The flow rate of the water to be supplied to the electrolytic cell may be defined so that the water to be treated can efficiently come into contact with the surface of an electrode or the like. , Because the contact with the dielectric and the particle surface is reduced,
It is preferable to form a turbulent state, and it is particularly preferable to form a turbulent flow having a Reynolds number of 500 or more.

前記電解層内を隔膜で区画して陽極室と陰極室を形成
しても、隔膜を使用せずにそのまま通電を行うこともで
きるが、隔膜を使用せずかつ電極の極間距離あるいは誘
電体と電極、又は誘電体相互の間隔を狭くする場合には
短絡防止のため電気絶縁性のスペーサとして例えば有機
高分子材料で作製した網状スペーサ等を両極間あるいは
前記誘電体間等に挿入することができる。又隔膜を使用
する場合には流通する被処理水の移動を妨害しないよう
に多孔質例えばその開口率が10％以上95％以下好ましく
は20％以上80％以下のものを使用することが望ましく、
該隔膜は少なくとも前記被処理水が透過できる程度の孔
径の微細孔を有していなければならない。Even if the anode layer and the cathode chamber are formed by partitioning the inside of the electrolytic layer with a diaphragm, energization can be carried out without using a diaphragm, but without using a diaphragm and the distance between the electrodes or the dielectric. In the case where the distance between the electrode and the dielectric or between the dielectrics is reduced, for example, a mesh spacer made of an organic polymer material or the like may be inserted between the electrodes or between the dielectrics as an electrically insulating spacer to prevent a short circuit. it can. When a diaphragm is used, it is desirable to use a porous material having an opening ratio of 10% or more and 95% or less, preferably 20% or more and 80% or less, so as not to hinder the movement of the water to be treated.
The diaphragm must have at least micropores with a pore size that allows the water to be treated to permeate.

このような構成から成る電解槽は、例えば浴場水の滅
菌用として使用する場合には、家庭用浴槽や銭湯や温泉
等の営業用浴場の浴槽あるいはこれらへの供給配管に接
続して、浴槽内の浴場水の全部又は一部を前記電解槽に
導入して電気化学的に処理することによりあるいは浴槽
に供給される前の水道水等を前記電解槽に供給して、前
記浴場水等の滅菌処理を行うことが出来、これにより浴
場水の清浄化が達成され、必要に応じてフィルタにより
不溶性物質を濾過することにより溶性及び不溶性の不純
物をほぼ完全に除去して使用済の浴場水を廃棄すること
なく長期に亘って使用して使用水量及びと燃料の節約を
達成することが出来る。When the electrolytic cell having such a configuration is used, for example, for sterilizing bath water, the electrolytic bath is connected to a bathtub of a commercial bath such as a home bathtub or a public bath or a hot spring, or a supply pipe to these bathtubs. Sterilizing the bath water by introducing all or a part of the bath water into the electrolytic bath and electrochemically treating the bath water or supplying tap water or the like before being supplied to the bath tub to the electrolytic bath; The treatment can be carried out, thereby purifying the bath water, and, if necessary, filtering the insoluble substances with a filter to almost completely remove the soluble and insoluble impurities and discarding the used bath water. It can be used over a long period of time without using water to save water and fuel consumption.

なお、本発明方法に使用する電解槽では該電解槽に漏
洩電流が生じ該漏洩電流が電解槽から被処理水を通して
他の部材に流れ込んで該部材の溶出等を起こすことがあ
るため、電解槽内の陽陰極が相対しない電極背面部及び
／又は前記電解槽の出入口配管内に、前記被処理液より
導電性の高い部材をその一端を接地可能なように設置し
て前記漏洩電流を遮断することができる。In the electrolytic cell used in the method of the present invention, a leakage current may be generated in the electrolytic cell, and the leakage current may flow from the electrolytic cell through the water to be treated to another member to cause elution of the member. A member having higher conductivity than the liquid to be treated is installed in the back surface of the electrode where the positive and negative electrodes do not face each other and / or in the inlet / outlet pipe of the electrolytic cell so that one end thereof can be grounded to cut off the leakage current. be able to.

次に添付図面に基づいて本発明に使用できる電解槽の
好ましい例を説明するが、本発明方法に使用されあるい
は本発明装置を構成する電解槽は、この電解槽に限定さ
れるものではない。Next, preferred examples of the electrolytic cell that can be used in the present invention will be described with reference to the accompanying drawings. However, the electrolytic cell used in the method of the present invention or constituting the apparatus of the present invention is not limited to this electrolytic cell.

第１図は、本発明方法の電解槽として使用可能な固定
床型複極式電解槽の一例を示す概略縦断面図である。FIG. 1 is a schematic vertical sectional view showing an example of a fixed-bed type bipolar electrolytic cell that can be used as an electrolytic cell in the method of the present invention.

上下にフランジ１を有する円筒形の電解槽本体２の内
部上端近傍及び下端近傍にはそれぞれメッシュ状の給電
用陽極ターミナル３と給電用陰極ターミナル４が設けら
れている。電解槽本体２は、長期間の使用又は再度の使
用にも耐え得る電気絶縁材料で形成することが好まし
く、特に合成樹脂であるポリエピクロルヒドリン、ポリ
ビニルメタクリレート、ポリエチレン、ポリプロピレ
ン、ポリ塩化ビニル、ポリ塩化エチレン、フェノール−
ホルムアルデヒド樹脂等が好ましく使用できる。正の直
流電圧を与える前記陽極ターミナル３は、例えば炭素材
（例えば活性炭、炭、コークス、石炭等）、グラファイ
ト材（例えば炭素繊維、カーボンクロス、グラファイト
等）、炭素複合材（例えば炭素に金属を粉状で混ぜ焼結
したもの等）、活性炭素繊維不織布（例えばKE−1000フ
ェルト、東洋紡株式会社）、又はこれに白金、白金、パ
ラジウムやニッケルを担持させた材料、更に寸法安定性
電極（白金族酸化物被覆チタン材）、白金被覆チタン
材、ニッケル材、ステンレス材、鉄材等から形成され
る。又陽極ターミナル３に対向し負の直流電圧を与える
陰極ターミナル４は、例えば白金、ステンレス、チタ
ン、ニッケル、銅、ハステロイ、グラファイト、炭素
材、軟鋼あるいは白金族金属をコーティングした金属材
料等から形成されている。A meshed power supply anode terminal 3 and a power supply cathode terminal 4 are provided near an upper end and a lower end of a cylindrical electrolytic cell main body 2 having upper and lower flanges 1, respectively. The electrolytic cell main body 2 is preferably formed of an electric insulating material that can withstand long-term use or re-use. Particularly, synthetic resins such as polyepichlorohydrin, polyvinyl methacrylate, polyethylene, polypropylene, polyvinyl chloride, and poly (ethylene chloride) are used. , Phenol-
Formaldehyde resins and the like can be preferably used. The anode terminal 3 for applying a positive DC voltage includes, for example, a carbon material (eg, activated carbon, charcoal, coke, coal, etc.), a graphite material (eg, carbon fiber, carbon cloth, graphite, etc.), a carbon composite material (eg, carbon Activated carbon fiber non-woven fabric (for example, KE-1000 Felt, Toyobo Co., Ltd.) or a material having platinum, platinum, palladium or nickel supported thereon, and a dimensionally stable electrode (platinum) Group oxide-coated titanium material), platinum-coated titanium material, nickel material, stainless steel material, iron material and the like. The cathode terminal 4 which faces the anode terminal 3 and gives a negative DC voltage is made of, for example, platinum, stainless steel, titanium, nickel, copper, hastelloy, graphite, carbon material, mild steel or a metal material coated with a platinum group metal. ing.

前記両電極ターミナル３、４間には複数個の図示の例
では３個のスポンジ状の固定床５が積層され、かつ該固
定床５間及び該固定床５と前記両電極ターミナル３、４
間に４枚の多孔質の隔膜あるいはスペーサー６が挟持さ
れている。各固定床５は電解槽本体２の内壁に密着し固
定床５の内部を通過せず、固定床５と電解槽本体２の側
壁との間を流れる被処理水の漏洩流がなるべく少なくな
るように配置されている。隔膜を使用する場合には該隔
膜として織布、素焼板、粒子焼結ブラスチック、多孔
板、イオン交換膜等が用いられ、スペーサーとして電気
絶縁性材料で製作された織布、多孔板、網、棒状材等が
使用される。In the illustrated example, a plurality of sponge-like fixed beds 5 are laminated between the two electrode terminals 3 and 4, and between the fixed beds 5 and between the fixed bed 5 and the two electrode terminals 3 and 4.
Four porous diaphragms or spacers 6 are sandwiched between them. Each fixed bed 5 is in close contact with the inner wall of the electrolytic cell main body 2, does not pass through the inside of the fixed bed 5, and the leakage flow of the water to be treated flowing between the fixed bed 5 and the side wall of the electrolytic cell main body 2 is minimized. Are located in When a diaphragm is used, a woven fabric, an unglazed plate, a particle sintered plastic, a perforated plate, an ion exchange membrane, or the like is used as the diaphragm, and a woven fabric, a perforated plate, a mesh made of an electrically insulating material is used as a spacer. , A rod-shaped material or the like is used.

このような構成から成る電解槽に下方から矢印で示す
ように例えば浴場水を供給しながら通電を行うと、前記
各固定床５が図示の如く下面に正に上面が負に分極して
固定床５内及び固定床５間に電位が生じ、該電解槽内を
流通する浴場水はこの電位を有する固定床５に接触して
その中に含有される黴や細菌の滅菌等の改質処理が行わ
れて該電解槽の上方から取り出される。When electricity is supplied to the electrolytic cell having such a configuration while supplying, for example, bath water as indicated by an arrow from below, the fixed beds 5 are polarized positively on the lower surface as shown in FIG. A potential is generated in the fixed bed 5 and between the fixed bed 5, and the bath water flowing in the electrolytic cell contacts the fixed bed 5 having this potential to perform a modification treatment such as sterilization of mold and bacteria contained therein. It is taken out from above the electrolytic cell.

第２図は、本発明に使用できる複極型固定床式電解槽
の他の例を示すもので、該電解槽は第１図の電解槽の固
定床５の給電用陰極４に向かう側つまり陽分極する側に
メッシュ状の不溶性金属材料７を密着状態で設置したも
のであり、他の部材は第１図と同一であるので同一符号
を付して説明を省略する。FIG. 2 shows another example of a bipolar type fixed-bed electrolytic cell which can be used in the present invention. The electrolytic cell is a side of the fixed bed 5 of the electrolytic cell of FIG. The mesh-shaped insoluble metal material 7 is installed in a state of close contact on the side to be positively polarized, and the other members are the same as those in FIG.

直流電圧が印加された固定床５はその両端部において
最も大きく分極が生じ、ガス発生が伴う場合には該両端
部において最も激しくガス発生が生ずる。従って最も強
く陽分極するつまり最も激しく酸素ガスが発生する固定
床５の給電用陰極４に向かう端部には最も速く溶解が生
じる。図示の通りこの部分に不溶性金属材料７を設置し
ておくと、該不溶性金属材料７の過電圧が固定床５を形
成する炭素系材料の過電圧より低いため殆どの酸素ガス
が前記不溶性金属材料７から発生し固定床５は殆ど酸素
ガスと接触しなくなるため、前記固定床５の溶解は効果
的に抑制される。又該電解槽２に供給された被処理水は
第１図の場合と同様に処理され滅菌が行われる。The fixed bed 5 to which the DC voltage is applied has the largest polarization at both ends, and when gas generation is involved, gas generation occurs most severely at both ends. Accordingly, the end of the fixed bed 5 toward the power supply cathode 4 of the fixed bed 5, which is the most strongly anodic polarized, that is, generates the most intense oxygen gas, dissolves fastest. As shown in the figure, when the insoluble metal material 7 is installed in this portion, most of the oxygen gas is removed from the insoluble metal material 7 because the overvoltage of the insoluble metal material 7 is lower than that of the carbon-based material forming the fixed bed 5. Since the generated fixed bed 5 hardly comes into contact with the oxygen gas, the dissolution of the fixed bed 5 is effectively suppressed. The water to be treated supplied to the electrolytic cell 2 is treated and sterilized as in the case of FIG.

第３図は、本発明に使用できる複極型固定床式電解槽
の他の例を示すものである。FIG. 3 shows another example of a bipolar fixed-bed electrolytic cell that can be used in the present invention.

上下にフランジ11を有する円筒形の電解槽本体12の内
部上端近傍及び下端近傍にはそれぞれメッシュ状の給電
用陽極13と給電用陰極14が設けられている。電解槽本体
12は、長期間の使用又は再度の使用にも耐え得る電気絶
縁材料特に合成樹脂で形成することが好ましい。A meshed power supply anode 13 and a power supply cathode 14 are provided near the upper end and the lower end of a cylindrical electrolytic cell main body 12 having a flange 11 at the top and bottom, respectively. Electrolyzer body
12 is preferably formed of an electrical insulating material that can withstand long-term use or re-use, especially a synthetic resin.

前記両給電用電極13、14間には、導電性材料例えば炭
素系材料で形成された多数の固定床形成用粒子15と該固
定床形成用粒子15より少数の例えば合成樹脂製の絶縁粒
子18とがほぼ均一に混在している。該絶縁粒子18は、前
記給電用陽極13及び給電用陰極14が完全に短絡すること
を防止する機能を有している。Between the power supply electrodes 13 and 14, a large number of fixed bed forming particles 15 formed of a conductive material such as a carbon-based material, and a smaller number of the fixed bed forming particles 15 such as insulating particles 18 made of a synthetic resin, for example. Are almost uniformly mixed. The insulating particles 18 have a function of preventing the power supply anode 13 and the power supply cathode 14 from being completely short-circuited.

このような構成から成る電解槽に下方から矢印で示す
ように被処理水を供給しながら通電を行うと、前記各固
定床形成用粒子15が給電用陽極13側が負に又給電用陰極
14側が正に分極して表面積が莫大な三次元電極として機
能し、第１図及び第２図の電解槽と同様にして前被処理
水中の黴や細菌等の微生物の滅菌等の改質処理が行われ
て該電解槽の上方から取り出される。When current is supplied to the electrolytic cell having such a configuration while supplying water to be treated as indicated by an arrow from below, each of the fixed bed forming particles 15 becomes negative on the power supply anode 13 side and the power supply cathode
The 14 side is positively polarized and functions as a three-dimensional electrode having a huge surface area. Similar to the electrolytic cell shown in FIGS. 1 and 2, modification treatment such as sterilization of microorganisms such as molds and bacteria in the pre-treatment water is performed. Is carried out and taken out from above the electrolytic cell.

第４図は、本発明に使用できる単極型固定床式電解槽
を例示するものである。FIG. 4 illustrates a monopolar fixed-bed electrolytic cell that can be used in the present invention.

上下にフランジ21を有する円筒形の電解槽本体22の内
部上端近傍及び下端近傍にはそれぞれメッシュ状の給電
用陽極23と給電用陰極24が設けられている。電解槽本体
22は、長期間の使用又は再度の使用にも耐え得る電気絶
縁材料特に合成樹脂で形成することが好ましい。A mesh-shaped power supply anode 23 and a power supply cathode 24 are provided near the upper end and the lower end of a cylindrical electrolytic cell main body 22 having upper and lower flanges 21, respectively. Electrolyzer body
22 is preferably formed of an electrical insulating material that can withstand long-term use or re-use, especially a synthetic resin.

前記両給電用電極23、24間には、隔膜26を挟んで導電
性材料例えば炭素繊維をフェルト状に成形した１対の固
定床25が陽極室内及び陰極室内に充填され、前記陽極室
内及び陰極室内のフェルト状炭素繊維はそれぞれ前記給
電用陽極23と給電用陰極24に電気的に接続され、陽極室
内の固定床は正に陰極室内の固定床は負に帯電されてい
る。A pair of fixed floors 25 made of a conductive material such as carbon fiber in a felt shape with a diaphragm 26 interposed therebetween is filled in the anode chamber and the cathode chamber between the power feeding electrodes 23 and 24, and the anode chamber and the cathode chamber are filled. The felt-like carbon fibers in the room are electrically connected to the power supply anode 23 and the power supply cathode 24, respectively, and the fixed floor in the anode room is positively charged and the fixed floor in the cathode room is negatively charged.

この電解槽に下方から矢印で示すように被処理水を供
給しながら通電を行うと、第１図から第３図の場合と同
様に固定床25が表面積が莫大な三次元電極として機能し
て被処理水中の黴や細菌等の微生物の滅菌等の改質処理
が行われて該電解槽の上方から取り出される。When electricity is supplied to this electrolytic cell while supplying water to be treated as shown by an arrow from below, the fixed bed 25 functions as a three-dimensional electrode having a huge surface area as in the case of FIGS. 1 to 3. The water to be treated is subjected to a modification treatment such as sterilization of microorganisms such as molds and bacteria, and is taken out from above the electrolytic cell.

（実施例） 次に本発明の被処理水の電気化学的処理方法の実施例
を記載するが、該実施例は本発明を限定するものではな
い。(Example) Next, an example of the electrochemical treatment method of the water to be treated of the present invention will be described, but the example does not limit the present invention.

実施例１ 透明な硬質ポリ塩化ビニル樹脂性の高さ100mm、内径5
0mmのフランジ付円筒形である第１図に示した電解槽
を、ポンプとともに家庭用浴槽に近接させて設置した。
該電解槽内には、炭素繊維から成る直径50mm、厚さ10mm
の固定床５個を、開口率80％で直径50mm及び厚さ1.2mm
のポリエチレン樹脂製隔膜６枚で挟み込み、上下両端の
隔膜にそれぞれ白金をその表面にメッキしたチタン製で
ある直径48mm厚さ1.0mmのメッシュ状給電用陽極及び陰
極を接触させて設置した。Example 1 A transparent rigid polyvinyl chloride resin having a height of 100 mm and an inner diameter of 5
The electrolytic cell shown in FIG. 1 having a cylindrical shape with a flange of 0 mm was installed close to a household bathtub together with a pump.
Inside the electrolytic cell, a diameter of 50 mm made of carbon fiber and a thickness of 10 mm
5 fixed floors with an aperture ratio of 80% and a diameter of 50 mm and a thickness of 1.2 mm
And a mesh-shaped power supply anode and cathode made of titanium having a diameter of 48 mm and a thickness of 1.0 mm, each of which is made of titanium plated with platinum on the upper and lower ends of the diaphragm.

41℃の浴場水を5l/分の速度で前記電解槽に供給し、
かつ前記給電用電極間に第１表に示す電解電圧を印加し
て前記浴場水の電気化学的処理を行った。該処理操作に
おける肉眼観察による発生ガスの有無、電解槽通過前後
の前記浴場水中の細菌数及び消費電力を第１表に纏め
た。Supply bath water at 41 ° C to the electrolytic cell at a rate of 5 l / min,
The electrolytic treatment shown in Table 1 was applied between the power supply electrodes to perform the electrochemical treatment of the bath water. Table 1 summarizes the presence / absence of generated gas by visual observation in the treatment operation, the number of bacteria in the bath water before and after passing through the electrolytic cell, and the power consumption.

実施例２ 固定床を形成する物質を変えたこと以外は、実施例１
の電解槽と同一の電解槽を使用し実施例１の電解条件で
細菌の個数が1825個/mlとなるように調製した被処理水
の処理を行った。なお電解槽の上下に被処理水の供給口
と排出口を設置した。Example 2 Example 1 except that the material forming the fixed bed was changed.
Using the same electrolyzer as the electrolyzer, the water to be treated was prepared under the electrolysis conditions of Example 1 so that the number of bacteria was 1825 / ml. A supply port and a discharge port for the water to be treated were provided above and below the electrolytic cell.

電解槽の固定床形成物質として第２表に示す物質をそ
れぞれ使用して、前記被処理水を2l/分 の速度で前記電解槽に供給し、かつ前記給電用電極間に
陽極電位＋1.0V（vs.SHE）及び陰極電位−0.6V（vs.SH
E）を印加して前記被処理水の電気化学的処理を行っ
た。該処理操作に使用した固定床形成物質を変化させた
場合の電解槽通過後の被処理水中の細菌数及び固定床の
腐食劣化状況を第２表に纏めた。Each of the substances shown in Table 2 was used as the fixed bed forming substance of the electrolytic cell, and the water to be treated was 2 l / min. To the electrolytic cell at a speed of, and between the power supply electrodes anode potential +1.0 V (vs. SHE) and cathode potential -0.6 V (vs. SH)
E) was applied to perform the electrochemical treatment of the water to be treated. Table 2 summarizes the number of bacteria in the water to be treated after passing through the electrolytic cell and the state of corrosion deterioration of the fixed bed when the fixed bed forming substance used in the treatment operation was changed.

第２表から明らかなように、固定床としての耐性を有
する物質は微生物の滅菌効果が顕著なこと が判る。As is evident from Table 2, substances having a fixed bed resistance have a remarkable microbial sterilization effect. I understand.

（発明の効果） 本発明方法は、水温が35℃以上である浴場水等の被処
理水を固定床型三次元電極電解槽に供給し、前記被処理
水を電気化学的に処理する方法である（請求項１）。(Effect of the Invention) The method of the present invention is a method of supplying treated water such as bath water having a water temperature of 35 ° C. or higher to a fixed-bed type three-dimensional electrode electrolytic cell, and electrochemically treating the treated water. (Claim 1).

本発明の対象とする被処理水例えば浴場水は最も微生
物の繁殖に適した35〜45℃の温度に維持されるため僅少
量の微生物が短時間で莫大な数に繁殖する。The water to be treated, for example, bath water, which is the object of the present invention, is maintained at a temperature of 35 to 45 ° C., which is most suitable for the propagation of microorganisms.

前記被処理水を固定床型三次元電極電解槽に供給する
と、該被処理水中の微生物は電位を与えられた陽極や陰
極あるいは誘電体や固定床形成用粒子等に接触しそれら
の表面で強力な酸化還元反応を受けたり高電位の電流に
接触し、その活動が弱まったり自身が死滅して滅菌が行
われる。When the water to be treated is supplied to the fixed-bed type three-dimensional electrode electrolytic cell, the microorganisms in the water to be treated come into contact with a potential-applied anode or cathode, a dielectric substance, particles for forming a fixed bed, or the like, and have a strong surface. It undergoes an oxidation-reduction reaction or comes into contact with a high-potential current, and its activity is weakened or it is killed and sterilization is performed.

従って本発明方法では、被処理水中の微生物が電圧印
加部分に接触すれば十分であり、両極間に電流を流して
水素及び酸素等のガス発生を伴う実質的な電解反応を生
起させることは必須ではなく、むしろ実質的な電解反応
が生じない低い電位を電極表面に印加することが好まし
い。これは実質的なガス発生が生じると被処理水成分に
ガス発生に起因する化学的変化を与えてしまい、これに
より複雑な作用が被処理液に起こることがあるからであ
りかつ電力を滅菌以外の不要なガス発生に使用する必要
がないからであるが、浴場水等では液組成の変化自体は
さほど問題が生じないのに対し、処理量が多いため電力
量の増大は出来る限り回避すべきである。従って本発明
方法では印加電位を陽極電位が実質的な酸素発生を伴わ
ない＋0.2〜＋1.2V（vs.SCE）、陰極電位が実質的に水
素発生を伴わない０〜−1.0V（vs.SCE）となるようにす
ることが望ましいが（請求項２）。Therefore, in the method of the present invention, it is sufficient that the microorganisms in the water to be treated come into contact with the portion to which voltage is applied, and it is essential that a current is applied between the two electrodes to cause a substantial electrolytic reaction accompanied by the generation of gas such as hydrogen and oxygen. Rather, it is preferable to apply a low potential to the electrode surface that does not cause a substantial electrolytic reaction. This is because, when substantial gas generation occurs, the water component to be treated undergoes a chemical change due to the gas generation, which may cause a complicated action in the liquid to be treated, and the electric power is not used for sterilization. This is because it is not necessary to use it for generating unnecessary gas.However, in bath water, etc., the change in the liquid composition itself does not cause much problem, but since the amount of treatment is large, an increase in power consumption should be avoided as much as possible. It is. Therefore, in the method of the present invention, the applied potential is set to +0.2 to +1.2 V (vs. SCE) where the anode potential does not substantially involve generation of oxygen, and 0 to -1.0 V (vs.) where the cathode potential does not substantially involve generation of hydrogen. .SCE) is desirable (claim 2).

本発明方法では表面積の大きい三次元電極を有する固
定床型三次元電極電解槽を使用するため、処理される被
処理水が十分に前記三次元電極と接触し、効率的に滅菌
等の処理が行われるが、三次元電極の中でも特に表面積
の大きい複極式固定床型三次元電極電解槽を使用すると
（請求項３）、処理効率が一層向上する。In the method of the present invention, since a fixed-bed type three-dimensional electrode electrolytic cell having a three-dimensional electrode having a large surface area is used, the water to be treated sufficiently contacts the three-dimensional electrode, and treatment such as sterilization can be efficiently performed. As described above, when a bipolar fixed bed type three-dimensional electrode electrolytic cell having a particularly large surface area is used among the three-dimensional electrodes (claim 3), the processing efficiency is further improved.

前記固定床型三次元電極電解槽の固定床を構成する材
料として、グラファイト、炭素系材料、活性炭等を使用
することが出来（請求項４）、これらの物質は比較的安
価で表面積が大きいため、本発明方法に使用される固定
床として有効である。As a material constituting the fixed bed of the fixed bed type three-dimensional electrode electrolytic cell, graphite, a carbon-based material, activated carbon, or the like can be used (claim 4). These materials are relatively inexpensive and have a large surface area. It is effective as a fixed bed used in the method of the present invention.

更に該固定床を複数個使用すると（請求項５）表面積
がより増大して処理効率が上昇する。Further, when a plurality of the fixed beds are used (claim 5), the surface area is further increased and the treatment efficiency is increased.

又35℃の水温を有する被処理水として浴場水を選択し
（請求項６）、銭湯や温泉等の営業用浴場や家庭用の浴
槽に近接して電解槽を設置し、浴場内の浴槽や家庭用浴
槽の浴場水の全部又は一部を前記電解槽に導入し電気化
学的に処理すると、微生物の繁殖に適した液温の前記浴
場水の滅菌処理を行うことが出来、これにより浴場水の
清浄化が達成され、必要に応じてフィルタにより不溶性
物質を濾過することにより溶性及び不溶性の不純物をほ
ぼ完全に除去して使用済の浴場水を廃棄することなく長
期に亘って使用して使用水量及びと燃料の節約を達成す
ることが出来る。In addition, bath water is selected as the water to be treated having a water temperature of 35 ° C. (Claim 6), and an electrolytic bath is installed in the vicinity of a commercial bath, a hot spring, or a commercial bath or a home bath, and a bath tub in the bath. When all or a part of the bath water in the home tub is introduced into the electrolytic bath and electrochemically treated, the bath water can be sterilized at a liquid temperature suitable for the propagation of microorganisms. Purification is achieved, and if necessary, soluble and insoluble impurities are removed almost completely by filtering insoluble substances through a filter, and used for a long time without disposing of used bath water. Water and fuel savings can be achieved.

【図面の簡単な説明】[Brief description of the drawings]

第１図、第２図、第３図及び第４図は、それぞれ本発明
方法に使用出来る固定床型三次元電極電解槽を例示する
ものである。 １……フランジ、２……電解槽本体 ３……給電用陽極ターミナル ４……給電用陰極ターミナル ５……固定床、６……スペーサー ７……不溶性金属材料 11……フランジ、12……電解槽本体 13……給電用陽極、14……給電用陰極 15……固定床形成用粒子、18……絶縁粒子 21……フランジ、22……電解槽本体 23……給電用陽極、24……給電用陰極 25……固定床、26……隔膜FIGS. 1, 2, 3 and 4 each illustrate a fixed-bed type three-dimensional electrode electrolytic cell which can be used in the method of the present invention. DESCRIPTION OF SYMBOLS 1 ... Flange 2 ... Electrolyzer main body 3 ... Power supply anode terminal 4 ... Power supply cathode terminal 5 ... Fixed floor, 6 ... Spacer 7 ... Insoluble metal material 11 ... Flange, 12 ... Electrolysis Tank body 13… Anode for power supply, 14… Cathode for power supply 15… Particles for forming fixed bed, 18… Insulated particles 21… Flange, 22… Electrolyzer body 23… Anode for power supply, 24… Power supply cathode 25: fixed bed, 26: diaphragm

───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.⁷，ＤＢ名) C02F 1/46 - 1/48 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C02F 1/46-1/48

Claims (7)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】微生物を含む被処理水を固定床型三次元電
極電解槽に供給し、前記被処理水中の微生物を多孔質か
つブロック状の前記電極に接触させ死滅させて該被処理
水を電気化学的に処理することを特徴とする被処理水の
処理方法。1. A method comprising the steps of: supplying water to be treated containing microorganisms to a fixed-bed type three-dimensional electrode electrolytic cell; contacting the microorganisms in the water to be treated with the porous and block-shaped electrode to kill the water; A method for treating water to be treated, wherein the treatment is performed electrochemically. 【請求項２】固定床型三次元電極電解槽の陽極電位が＋
0.2〜＋1.2V（vs.SHE）で陰極電位が０〜−1.0V（vs.SH
E）である請求項１に記載の処理方法。2. The anode potential of a fixed bed type three-dimensional electrode electrolytic cell is +
0.2 to +1.2 V (vs. SHE) and the cathode potential is 0 to -1.0 V (vs. SHE)
The processing method according to claim 1, which is E). 【請求項３】固定床型三次元電極電解槽が、電圧の印加
により陽陰極に分極する固定床内を被処理水が流通する
複極式固定床型三次元電極電解槽である請求項１又は２
に記載の処理方法。3. The fixed-bed type three-dimensional electrode electrolyzer is a bipolar fixed-bed type three-dimensional electrode electrolyzer in which water to be treated flows in a fixed bed which is polarized into a positive electrode by application of a voltage. Or 2
The processing method described in 1. 【請求項４】固定床型三次元電極電解槽の固定床がグラ
ファイト、炭素系材料、活性炭及び金属から成る群から
選択される材料で構成される請求項１から３までのいず
れかに記載の処理方法。4. The fixed bed of a fixed bed type three-dimensional electrode electrolytic cell according to claim 1, wherein the fixed bed is made of a material selected from the group consisting of graphite, carbon-based material, activated carbon and metal. Processing method. 【請求項５】固定床型三次元電極電解槽が、給電用陽陰
極間に、陽陰極に分極する複数個の固定床を設置した電
解槽である請求項１から４までのいずれかに記載の処理
方法。5. The fixed bed type three-dimensional electrode electrolytic cell according to claim 1, wherein a plurality of fixed beds polarized between the positive and negative electrodes for power supply are installed between the positive and negative electrodes for power supply. Processing method. 【請求項６】被処理水が浴場水である請求項１から５ま
でのいずれかに記載の処理方法。6. The treatment method according to claim 1, wherein the water to be treated is bath water. 【請求項７】被処理水の温度が35℃以上である請求項１
から６までのいずれかに記載の処理方法。7. The temperature of the water to be treated is 35 ° C. or higher.
7. The processing method according to any one of to 6.