JPH08173972A - Porous carbon electrode for water treatment and manufacture of the same - Google Patents

Abstract

PURPOSE: To provide a porous carbon electrode which lowers a corrosion current in electrochemical water treatment, has high metal recovery capacity and flexural strength, and can be produced easily. CONSTITUTION: An electrode in which carbon fibers are combined integrally with an organic polymer such as a phenol resin contains a carbon fine powder as necessity requires. In a method for producing a porous carbon electrode, sheets of carbon fibers or organic polymer fibers which are converted into carbon fibers by carbonization are impregnated with an organic polymer, preferably a liquid thermosetting resin, laminated, and carbonized by heating.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、水中に存在する微生物
を電気化学的方法（電解）により殺菌するための水処理
用、あるいは金属イオンを含む水溶液から電解により金
属を回収するための水処理用多孔質炭素電極及びその製
造法に関する。FIELD OF THE INVENTION The present invention relates to a water treatment for sterilizing microorganisms existing in water by an electrochemical method (electrolysis), or a water treatment for recovering a metal from an aqueous solution containing metal ions by electrolysis. And a method for producing the same.

【０００２】[0002]

【従来の技術】飲料水、浴場やプール水、工業設備の冷
却水、防火用水、食品工場の各種水洗水等における微生
物（菌類、原生動物、藻類、藍藻類、細菌）の殺菌には
薬剤添加、紫外線照射、加熱等の手段が採られている
が、殺菌効率が悪かったり、抗菌が増殖する等の問題が
ある。そこで最近は微生物を特殊な電解槽の中で殺菌す
る方法が提案されている。また写真の現像、定着におけ
る処理液には銀イオン等が含まれ、またメッキの水洗廃
液には微量の貴金属イオンが含まれている。その他各種
の廃液の中に重金属イオンが微量に含まれる場合があ
る。これらの貴金属や重金属を有効利用あるいは環境問
題等から回収する必要が生ずる。この電解回収にも上記
した微生物の殺菌に用いられるのと同じ特殊な電解槽が
有効であることが知られている。2. Description of the Related Art Addition of chemicals to sterilize microorganisms (fungi, protozoa, algae, cyanobacteria, bacteria) in drinking water, bath and pool water, cooling water for industrial equipment, fire prevention water, various kinds of washing water in food factories, etc. However, there are problems such as poor sterilization efficiency and proliferation of antibacterial, although measures such as ultraviolet irradiation and heating are adopted. Therefore, recently, a method of sterilizing microorganisms in a special electrolytic cell has been proposed. Further, the processing solution in the development and fixing of the photograph contains silver ions and the like, and the washing waste liquid of the plating contains a trace amount of precious metal ions. Other various waste liquids may contain trace amounts of heavy metal ions. It is necessary to effectively use these precious metals and heavy metals or to recover them from environmental problems. It is known that the same special electrolytic cell as that used for the sterilization of the above-mentioned microorganisms is also effective for this electrolytic recovery.

【０００３】これらの水処理方法の概略を図１に、その
方法に用いられる電解槽の構成を図２に示す。図１にお
いて、１は被処理液貯槽、２は被処理液を電解槽に供給
するポンプ、３はゴミを除去するためのフィルターであ
る。電解槽４には直流電源５が接続され、通常液の入口
側が陽極、出口側が負極とされる。処理を繰り返す場合
は電解槽で処理された液は再び貯槽１に戻り、必要な回
数だけ循環処理される。図で６，７は電解槽への流量を
所定値にするための弁、８，９は電解槽の性能を調べる
ためのサンプリング弁である。FIG. 1 shows an outline of these water treatment methods, and FIG. 2 shows the constitution of an electrolytic cell used in the method. In FIG. 1, 1 is a storage tank for liquid to be treated, 2 is a pump for supplying the liquid to be treated to an electrolytic bath, and 3 is a filter for removing dust. A direct current power supply 5 is connected to the electrolytic cell 4, and the inlet side of the normal solution is the anode and the outlet side is the negative electrode. When the treatment is repeated, the liquid treated in the electrolytic bath returns to the storage tank 1 and is circulated as many times as necessary. In the figure, 6 and 7 are valves for setting the flow rate to the electrolytic cell to a predetermined value, and 8 and 9 are sampling valves for examining the performance of the electrolytic cell.

【０００４】図２は電解槽で４１が筐体、４２は直流電
圧印加端子、４３は金属多孔板のターミナル電極、４４
は電極間距離を一定に保つためのスペーサー、４５は多
孔質炭素電極板である。スペーサーと多孔質炭素電極板
はセットとなり多数積層される。４６は液の入口（陽極
側）、４７は液の出口（陰極側）である。この電解槽に
微生物を含む水を通し、電圧を印加することにより、微
生物の殺菌が行なわれる。その際の作用機構は処理液中
の微生物が陽極表面に吸着され、電流を受けることで電
解反応を生じて死滅するといわれている。金属イオンを
含む水溶液の処理では多孔質炭素電極板の陰極側に金属
が析出するので、その量がある程度以上になったところ
で電極板を取外し、種々の方法で金属を回収する。FIG. 2 shows an electrolytic cell, in which 41 is a housing, 42 is a DC voltage applying terminal, 43 is a metal porous plate terminal electrode, and 44 is a metal porous plate terminal electrode.
Is a spacer for keeping the distance between electrodes constant, and 45 is a porous carbon electrode plate. A large number of spacers and porous carbon electrode plates are stacked as a set. Reference numeral 46 is a liquid inlet (anode side), and 47 is a liquid outlet (cathode side). Microorganisms are sterilized by passing water containing microorganisms through the electrolytic cell and applying a voltage. It is said that the mechanism of action at that time is that the microorganisms in the treatment liquid are adsorbed on the surface of the anode and receive an electric current to cause an electrolytic reaction to die. In the treatment of the aqueous solution containing metal ions, metal is deposited on the cathode side of the porous carbon electrode plate, so when the amount exceeds a certain level, the electrode plate is removed and the metal is recovered by various methods.

【０００５】これらの電解槽に使用される炭素電極は殺
菌作用や金属の析出能が高いのが望ましく、また電解に
よって陽極側に酸素が発生し、電極の腐食が起こるの
で、耐食性の高い材料が望ましい。この電解槽に用いら
れる多孔質炭素電極として特開昭６４−７０１８８、特
開平１−１９３５３８、特開平２−１９１５８８、特開
平５−１５４４８８、特開平６−８６９８１、特開平６
−８６９８３等に粒状、球状、フェルト状、織布状、多
孔質ブロック状、多数の貫通孔を形成した中実体等の形
状を有する活性炭、グラファイト、炭素繊維等の炭素系
材料が記載されている。しかし、これらの公報には粒状
や繊維状の炭素系材料をどのようにして炭素電極に成形
するかの具体的な方法は記載されていない。その他炭素
粒状物を主体とし、これにピッチあるいは樹脂を添加
し、成形、焼成、黒鉛化して多孔質炭素電極を製造する
場合、炭素粒状物の粒度を揃えて炭素電極の気孔率を上
げる方法もある（東海カーボン（株）製：商品記号Ｇ１
００Ｓ）。It is desirable that the carbon electrodes used in these electrolytic cells have a high sterilizing action and a high metal deposition ability. Further, since electrolysis causes oxygen to be generated on the anode side and causes corrosion of the electrodes, a material having high corrosion resistance should be used. desirable. As a porous carbon electrode used in this electrolytic cell, JP-A-64-70188, JP-A-1-193538, JP-A-2-191588, JP-A-5-154488, JP-A-6-86981, and JP-A-6-86981.
-86983 and the like describe carbonaceous materials such as granular, spherical, felt-like, woven cloth-like, porous block-like, solid bodies having a large number of through holes, activated carbon, graphite, carbon fiber and the like. . However, these publications do not describe a specific method of forming a granular or fibrous carbonaceous material into a carbon electrode. In the case of producing a porous carbon electrode by mainly using other carbon particles and adding pitch or resin to them, molding, firing, and graphitizing, a method of increasing the porosity of the carbon electrode by making the particle sizes of the carbon particles uniform is also available. There (product code G1 manufactured by Tokai Carbon Co., Ltd.)
00S).

【０００６】[0006]

【発明が解決しようとする課題】通常のグラファイト電
極の材質では、この水処理電解に用いられる電極として
は腐食電流が大きく、使用中に電極の崩落が起こる。炭
素繊維は腐食電流が小さく、この点では優れた材料であ
るが、上記したフェルト状、織布状では電気抵抗が大き
いという問題がある。また水処理における殺菌や金属の
回収効果についても十分ではない。炭素粒状物の粒度を
揃えて気孔率を上げる方法では粒状物（通常の黒鉛）が
主体であって、上記した腐食電流が大きいという問題が
ある他、気孔率も５０％程度が限度であり水処理におけ
る殺菌作用も低い。また気孔率の割には曲げ強度も弱
い。本発明の目的は電気化学的な水処理における腐食電
流が小さく、殺菌作用、金属回収能及び曲げ強度が大き
く、かつ容易に製造可能な多孔質炭素電極及びその製造
法を提供することにある。With the materials of ordinary graphite electrodes, the electrodes used in this water treatment electrolysis have a large corrosion current, and the electrodes collapse during use. Carbon fiber has a small corrosion current and is an excellent material in this respect, but there is a problem in that the above-mentioned felt shape and woven cloth shape have a large electric resistance. Moreover, the effect of sterilization and metal recovery in water treatment is not sufficient. In the method of increasing the porosity by making the particle sizes of the carbon particles uniform, the particles (normal graphite) are mainly used, and there is a problem that the above-mentioned corrosion current is large, and the porosity is limited to about 50%. The bactericidal action in processing is also low. In addition, bending strength is weak relative to porosity. An object of the present invention is to provide a porous carbon electrode having a small corrosion current in electrochemical water treatment, a large bactericidal action, a metal recovering ability and a large bending strength, and easily manufactured, and a method for manufacturing the same.

【０００７】[0007]

【課題を解決するための手段】本発明は、電気化学的
（電解）水処理における炭素電極の材質について種々研
究した結果到達したもので、その要旨は炭素繊維を有機
高分子物質の炭化物で一体に結合したことを特徴とする
電気化学的な水処理用多孔質炭素電極にある。炭素繊維
を水処理の電極に使用することは先に述べたように公知
である。しかし、従来の炭素繊維はフェルト状や織布等
で使用されているので電気抵抗が大きかったり、取扱い
に不便であるなどの問題があった。これに対し、本発明
の電極は炭素繊維を有機高分子物質の炭化物で一体に結
合しているので、電気抵抗も小さくなり、また曲げ強度
等も大きく取扱い易い。さらに有機高分子物質の種類に
よりその炭化物をガラス状とすることができ、それによ
って水処理の殺菌の効果も大きくなる。The present invention has been reached as a result of various researches on the material of the carbon electrode in the electrochemical (electrolytic) water treatment, and the gist thereof is to integrate the carbon fiber with a carbide of an organic polymer substance. The porous carbon electrode for electrochemical water treatment is characterized in that it is bonded to. The use of carbon fibers in electrodes for water treatment is known as mentioned above. However, since the conventional carbon fibers are used in the form of felt or woven fabric, there are problems that they have a large electric resistance and are inconvenient to handle. On the other hand, in the electrode of the present invention, the carbon fibers are integrally bonded by the carbide of the organic polymer substance, so that the electric resistance becomes small, and the bending strength and the like become large and easy to handle. Further, depending on the kind of the organic polymer substance, the carbide can be made glassy, and thereby the sterilizing effect of the water treatment is enhanced.

【０００８】炭素繊維としては通常のＰＡＮ（ポリアク
リロニトリル）系、ピッチ系、フェノール樹脂系、ビニ
ロン系、セルロース系などの有機高分子繊維からつくら
れた炭素繊維が使用できる。この炭素繊維には既に炭素
繊維となっているものを用いて、これを有機高分子物質
の炭化物で一体にしたもの及び有機高分子繊維を用い、
有機高分子物質の炭化の際に同時に炭化して繊維とした
ものも含まれる。有機高分子繊維の場合、ＰＡＮ系やピ
ッチ系では炭化の前に不融化処理が必要であるが、パル
プ、レーヨン等のセルロース系は不融化処理が必要でな
く、また抄紙によって容易にシートとすることができる
など製造上も有利である。またセルロース系及びＰＡＮ
系の炭素繊維はガラス状炭素となり、他の炭素繊維に較
べ水処理における殺菌効果が大きいなど好ましい炭素繊
維である。As the carbon fiber, a carbon fiber made of a normal PAN (polyacrylonitrile) type, pitch type, phenol resin type, vinylon type, cellulose type or other organic polymer fiber can be used. For this carbon fiber, one that has already become a carbon fiber is used, and one obtained by integrating it with a carbide of an organic polymer substance and an organic polymer fiber are used.
Fibers that are carbonized simultaneously with the carbonization of the organic polymer are also included. In the case of organic polymer fibers, PAN-based and pitch-based fibers require infusibilizing treatment before carbonization, but cellulose-based materials such as pulp and rayon do not require infusibilizing treatment, and are easily made into sheets by papermaking. It is also advantageous in terms of manufacturing. Also cellulosic and PAN
The carbon fibers of the system are glassy carbon, and are preferable carbon fibers because they have a greater sterilizing effect in water treatment than other carbon fibers.

【０００９】炭素繊維を一体に結合するのに用いられる
有機高分子物質はフェノール樹脂、フラン樹脂、ジビニ
ルベンゼン等の熱硬化性樹脂やポリ塩化ビニル、ポリア
クリロニトリル、ポリカルボジイミド、石炭ピッチ等の
炭化時の残炭率の高い有機高分子物質である。この中で
特に炭化したものがガラス状炭素となる熱硬化性樹脂が
好ましい。電解による水処理に用いられる電極は、通常
は板状に成形され板に直角方向に通水される。この際に
水が電極内に一様に分散していることが望ましく、それ
には水が板厚方向よりも板に平行な方向に流れ易くした
方がよい。それによって通水経路が長くなるからであ
る。Organic polymeric substances used for integrally bonding carbon fibers are thermosetting resins such as phenol resin, furan resin and divinylbenzene, carbonization of polyvinyl chloride, polyacrylonitrile, polycarbodiimide and coal pitch. It is an organic polymer substance with a high residual coal rate. Of these, a thermosetting resin in which carbonized one becomes glassy carbon is particularly preferable. An electrode used for water treatment by electrolysis is usually formed in a plate shape and water is passed through the plate in a direction perpendicular to the plate. At this time, it is desirable that the water be uniformly dispersed in the electrode, and it is better for the water to flow in the direction parallel to the plate rather than the plate thickness direction. This is because the water passage becomes longer.

【００１０】本発明の多孔質炭素電極は炭素繊維が含ま
れており、成形の際に炭素繊維が板に平行に揃い易く、
そのために板に平行方向と直角方向で異方性があり、こ
れを通気性で表わすと平行方向が直角方向に対し、１．
３倍以上通気率が大きい。通気率で表わしたのは通水率
よりも測定のバラツキが少なく正確に表わせるからであ
る。電極中に含まれる炭素繊維は４５〜６５重量％が適
当である。これよりも少ないと気孔率が小さくなり、ま
た電気抵抗が大きくなる。さらに成形上も不利となるば
かりでなく曲げ強度も劣る。また炭素繊維が多過ぎると
有機高分子物質の炭化物が少なくなり、成形体を一体結
合する上で支障をきたす。The porous carbon electrode of the present invention contains carbon fibers, and it is easy to align the carbon fibers parallel to the plate during molding.
Therefore, the plate has anisotropy in the direction parallel to the direction perpendicular to the direction parallel to the direction perpendicular to the direction perpendicular to the direction.
Greater than 3 times the air permeability. The air permeability is expressed because it has less variation in measurement than the water permeability and can be expressed accurately. The carbon fiber contained in the electrode is preferably 45 to 65% by weight. If it is less than this range, the porosity decreases and the electric resistance increases. In addition to being disadvantageous in terms of molding, the bending strength is also poor. Further, if the carbon fibers are too much, the amount of carbides of the organic polymer substance will decrease, which will be an obstacle to integrally bonding the molded bodies.

【００１１】電極中の残部は有機高分子物質の炭化物で
あるが、さらに炭素微粉を含有させることもできる。炭
素微粉を含有させることで電気抵抗が小さくなる効果が
あるが、多過ぎると気孔率が小さくなったり、また水処
理における殺菌等の効果が劣るので１５重量％以下が好
ましい。炭素微粉としては粒度１０μｍ以下程度の黒鉛
微粉や炭素繊維の粉末が好ましい。これらの炭素繊維、
有機高分子物質の炭化物、炭素微粉の組成割合の特に好
ましい範囲をあげれば、炭素繊維４０〜６５重量％、有
機高分子物質の炭化物３５〜６０重量％、炭素微粉０〜
１５重量％である。The balance in the electrode is a carbide of an organic polymer substance, but carbon fine powder can be further contained. The addition of the fine carbon powder has the effect of reducing the electric resistance, but when the amount is too large, the porosity decreases and the effect of sterilization in water treatment is deteriorated, so 15% by weight or less is preferable. The fine carbon powder is preferably fine graphite powder or carbon fiber powder having a particle size of about 10 μm or less. These carbon fibers,
To give a particularly preferable range of the composition ratio of the carbide of the organic polymer substance and the carbon fine powder, 40 to 65% by weight of the carbon fiber, 35 to 60% by weight of the carbide of the organic polymer substance, and the carbon fine powder 0 to
15% by weight.

【００１２】炭素電極、特に陽極は電解作用により発生
期の陰イオン（酸化剤）に晒され、消耗するので一定以
上の耐食性が求められる。また微生物は一般にマイナス
荷電を帯びており、炭素陽極近傍で殺菌されるため、炭
素陽極の耐食性は重要なファクターである。耐食性が劣
ると炭素電極の崩落等により消耗が加速される。この耐
食性は電気化学的手法で求められる腐食電流で評価する
ことができる。本発明では短時間で評価するために腐食
性の極めて強い高温リン酸中での腐食電流値を多孔質炭
素電極の耐食性評価の指標とした。The carbon electrode, particularly the anode, is exposed to the anion (oxidizing agent) in the nascent stage by the electrolytic action and is consumed, so that a certain level of corrosion resistance is required. Since microorganisms are generally negatively charged and sterilized in the vicinity of the carbon anode, the corrosion resistance of the carbon anode is an important factor. If the corrosion resistance is inferior, the consumption is accelerated due to the collapse of the carbon electrode. This corrosion resistance can be evaluated by the corrosion current required by an electrochemical method. In the present invention, in order to evaluate in a short time, the corrosion current value in high-temperature phosphoric acid, which is extremely corrosive, is used as an index for evaluating the corrosion resistance of the porous carbon electrode.

【００１３】本発明の炭素電極は、炭素繊維が有機高分
子物質の炭化物で一体に結合されているため耐食性がよ
く、腐食電流は好ましくは１０μＡｍｐ／ｃｍ² （２０
０℃、９５％リン酸液中）以下であり、特に有機高分子
物質の炭化物がガラス状炭素の場合はさらに好ましい５
μＡｍｐ／ｃｍ² 以下とすることもできる。この腐食電
流が１０μＡｍｐ／ｃｍ² を越えると水処理の電解槽に
使用した場合、数日間の通電後に目視で崩落が観察でき
る位に消耗が起こる。The carbon electrode of the present invention has good corrosion resistance because the carbon fibers are integrally bonded by the carbide of the organic polymer, and the corrosion current is preferably 10 μAmp / cm ² (20
0 ° C., in 95% phosphoric acid solution) or less, and particularly preferable when the organic polymer carbide is glassy carbon 5
It can also be set to μAmp / cm ² or less. If this corrosion current exceeds 10 μAmp / cm ² , when used in an electrolytic cell for water treatment, it will be consumed to such an extent that a collapse can be visually observed after energization for several days.

【００１４】多孔質炭素電極は電気比抵抗が低いことが
求められる。電気比抵抗が高いと電解槽の電気エネルギ
ー効率が下がるばかりでなく、電気化学現象に一般に観
察されるように電解分極電圧が大きくなり電流が効率よ
く透過水中に流れなくなり、殺菌効率が低下する。本発
明の炭素電極は炭素繊維を導電性の炭化物で一体に結合
しているので炭素繊維の織布やフェルトに較べ電気抵抗
は低く、好ましくは２０ｍΩｃｍ以下、さらに好ましく
は１０ｍΩｃｍ以下である。電気抵抗が２０ｍΩｃｍを
越えると前記の分極電圧が大きくなる。The porous carbon electrode is required to have a low electric resistivity. When the electric resistivity is high, not only the electric energy efficiency of the electrolytic cell is lowered, but also the electrolytic polarization voltage is increased as generally observed in the electrochemical phenomenon, so that the current does not efficiently flow into the permeate and the sterilization efficiency is lowered. In the carbon electrode of the present invention, since carbon fibers are integrally bonded with a conductive carbide, the electric resistance is lower than that of a woven fabric or felt of carbon fibers, preferably 20 mΩcm or less, more preferably 10 mΩcm or less. When the electric resistance exceeds 20 mΩcm, the polarization voltage increases.

【００１５】殺菌効率は被処理水とこれが透過する多孔
質炭素電極との接触面積が大きい程高くなる。即ち多孔
質炭素電極の気孔率が大きい程効率は高くなる。また気
孔径は透過水の偏流が発生しにくい均一な分布をしてい
ることが好ましい。気孔径の大きさは透過水中の微生物
の拡散性を考慮し、かつ処理量及び処理速度を勘案した
適当な大きさでなければならない。多孔質炭素電極の気
孔径は３０〜９０μｍの大きさが好ましい。気孔径が３
０μｍ以下では微生物による気孔の閉塞が発生し易く、
また９０μｍ以上のような大きな気孔径では透過水中の
微生物と炭素材との接触頻度が減少し、殺菌効率が低下
する。本発明者が詳細に検討した結果、本発明の多孔質
炭素電極は気孔率が５０％以上、気孔径はその８０％以
上が３０〜９０μｍ（水銀圧入法）に分布していること
が好ましい。気孔率は高過ぎると曲げ強度が弱くなるの
で、上限は７５％程度が適する。気孔は殆どが開気孔で
ある。The sterilization efficiency increases as the contact area between the water to be treated and the porous carbon electrode through which the water permeates increases. That is, the higher the porosity of the porous carbon electrode, the higher the efficiency. Further, it is preferable that the pore diameter has a uniform distribution in which permeated water is less likely to drift. The size of the pore size must be an appropriate size in consideration of the diffusibility of microorganisms in the permeate and the amount and speed of treatment. The pore diameter of the porous carbon electrode is preferably 30 to 90 μm. Pore size is 3
When it is 0 μm or less, pores are easily blocked by microorganisms,
Further, if the pore size is large, such as 90 μm or more, the frequency of contact between the microorganisms in the permeate and the carbonaceous material decreases, and the sterilization efficiency decreases. As a result of detailed study by the present inventor, it is preferable that the porous carbon electrode of the present invention has a porosity of 50% or more and a pore diameter of 80% or more of 30 to 90 μm (mercury intrusion method). If the porosity is too high, the bending strength becomes weak, so an upper limit of about 75% is suitable. Most of the pores are open pores.

【００１６】多孔質炭素電極の通水性は気孔率及び気孔
径と関係している。気孔率が大きい程、また気孔径が大
きい程通水性は高くなる。通水性は被処理水の処理能力
と関係している重要なファクターであり、通水性が低い
と処理能力が低くなり装置自体の実用を難しくする。詳
細に検討した実用可能な多孔質炭素材の通水性は通気率
で表わすと好ましくは２，０００ｍｌ・ｍｍ／ｈｒ／ｃ
ｍ² ／ｍｍＡｑ以上であり、さらに好ましくは４，００
０ｍｌ・ｍｍ／ｈｒ／ｃｍ² ／ｍｍＡｑ以上である。通
水率の測定は差圧計、その配管等々により測定値の誤差
を発生し易いので、本発明の記述においては測定が容易
で測定値の信頼性が高い通気率（空気の通気性）を通水
性の代替指標とした。本発明の多孔質炭素電極は電解槽
の一部品として使用されるので、もちろん装置部品とし
ての機械強度が求められる。機械強度としては曲げ強さ
＝４０ｋｇ／ｃｍ² 以上あれば十分に使用可能である。The water permeability of the porous carbon electrode is related to the porosity and the pore diameter. The larger the porosity and the larger the pore diameter, the higher the water permeability. Water permeability is an important factor related to the treatment capacity of the water to be treated, and if the water permeability is low, the treatment capacity will be low, making the device itself difficult to put into practical use. The water permeability of a practicable porous carbon material which has been studied in detail is preferably 2,000 ml · mm / hr / c, when expressed in terms of air permeability.
m ² / mmAq or more, more preferably 4,000
It is 0 ml · mm / hr / cm ² / mmAq or more. Since the measurement of the water flow rate is likely to cause an error in the measurement value due to the differential pressure gauge, its piping, etc., in the description of the present invention, the ventilation rate (air permeability) which is easy to measure and has high reliability of the measurement value is used. It was used as a water-based alternative index. Since the porous carbon electrode of the present invention is used as a part of an electrolytic cell, it is of course required to have mechanical strength as a device part. As for mechanical strength, bending strength of 40 kg / cm ² or more is sufficient for use.

【００１７】次に製造法の発明について説明する。炭素
繊維又は炭化により炭素繊維となる有機高分子繊維は前
記した繊維が用いられる。これらの繊維をシートに成形
する。シート化の最も好ましい方法は抄紙法である。繊
維は殺菌の性能上は細い程好ましいと思われるが、抄紙
上の点も勘案し、太さが５〜２０デニール、長さが２〜
２０ｍｍ程度が適当である。抄紙においては操作をし易
くするために少量のポリビニルアルコール、ビニロン等
の市販されているバインダーを使用する。さらにシート
の強度を増すため少量のエポキシ樹脂等を加えることも
できる。繊維がパルプ以外の場合は別に少量のパルプを
添加することが好ましい。また抄紙工程における液中に
炭素粉末を分散させることにより、あるいはシートに有
機高分子物質を含浸する際、その物質に炭素粉末を添加
することによりシートに炭素粉末を含有させることがで
きる。繊維は上記のように既に炭素繊維となっているも
のも使用可能であるが、炭素繊維は高価であるので経済
的には有機高分子繊維が有利である。Next, the invention of the manufacturing method will be described. The aforementioned fibers are used as the carbon fibers or the organic polymer fibers that become carbon fibers by carbonization. These fibers are formed into sheets. The most preferred method of making a sheet is a papermaking method. It seems that the thinner the fiber, the more preferable it is in terms of sterilization performance, but in consideration of the papermaking point, the fiber has a thickness of 5 to 20 denier and a length of 2 to 2.
About 20 mm is suitable. In papermaking, a small amount of a commercially available binder such as polyvinyl alcohol or vinylon is used to facilitate the operation. Furthermore, a small amount of epoxy resin or the like can be added to increase the strength of the sheet. When the fiber is other than pulp, it is preferable to add a small amount of pulp separately. Further, the carbon powder can be contained in the sheet by dispersing the carbon powder in the liquid in the papermaking process or by adding the carbon powder to the substance when impregnating the sheet with the organic polymer substance. As the fiber, it is possible to use a fiber which is already a carbon fiber as described above, but since the carbon fiber is expensive, the organic polymer fiber is economically advantageous.

【００１８】有機高分子繊維を使用した場合のシートの
望ましい例を示せば、有機高分子繊維６０〜９０重量
部、パルプ３〜３５重量部、抄紙用バインダー２〜２０
重量部、これらの合計１００重量部に対し炭素微粉０〜
１８重量部である。有機高分子繊維の中では前記のよう
にセルロース系やＰＡＮ系の繊維が水処理における殺菌
効果が高く好ましい繊維であり、さらに不融化処理を必
要としない点でセルロース系繊維が特に好ましい繊維で
ある。If a preferable example of the sheet using organic polymer fibers is shown, 60 to 90 parts by weight of organic polymer fibers, 3 to 35 parts by weight of pulp, and binders 2 to 20 for papermaking are used.
Parts by weight, carbon fine powder 0 to 100 parts by weight in total.
18 parts by weight. Among the organic polymer fibers, the cellulosic fiber and the PAN fiber are preferable fibers because of their high bactericidal effect in water treatment as described above, and the cellulosic fiber is particularly preferable fiber because it does not require infusibilizing treatment. .

【００１９】シートにはフェノール樹脂、フラン樹脂、
ジビニルベンゼン、塩化ビニル、アクリロニトリル、ポ
リカルボジイミド、石炭ピッチ等の有機高分子物質ある
いは加熱等により重合して有機高分子となるプレポリマ
ー等の物質（本明細書ではこれらを総合して有機高分子
物質と呼ぶ）の液体を含浸する。含浸は例えばシートを
これらの含浸液体に浸漬して行なう。含浸液は溶剤を添
加したりあるいは加熱して粘度を調整することができる
が、室温で取扱い易い液状のフェノール樹脂、フラン樹
脂等の熱硬化性樹脂が好ましい。また前記したように熱
硬化性樹脂は炭化によりガラス状炭素となり、水処理に
おける殺菌効果が高く、また強度も大きく特に望ましい
樹脂である。The sheet includes phenol resin, furan resin,
Organic polymeric substances such as divinylbenzene, vinyl chloride, acrylonitrile, polycarbodiimide, and coal pitch, or substances such as prepolymers that are polymerized by heating or the like to form organic polymers (in the present specification, these are collectively referred to as organic polymeric substances). (I call it) liquid. Impregnation is carried out, for example, by immersing the sheet in these impregnating liquids. Although the viscosity of the impregnating solution can be adjusted by adding a solvent or heating the impregnating solution, a thermosetting resin such as a liquid phenol resin or furan resin which is easy to handle at room temperature is preferable. Further, as described above, the thermosetting resin becomes a glassy carbon due to carbonization, has a high bactericidal effect in water treatment, and has a large strength, and is a particularly desirable resin.

【００２０】含浸したシートはこれを積層し、加圧成形
される。含浸液が熱硬化性樹脂の場合は１５０〜２５０
℃程度に加熱しながら加圧成形するのが好ましい。シー
ト中の含浸液の量は含浸液の濃度、浸漬条件、さらには
積層における加圧力によって調整される。加圧の圧力は
大き過ぎると多孔質炭素板の気孔率が低下し、低過ぎる
と樹脂含浸シート間の接着性に支障をきたすので一般的
には０．５〜１０ｋｇ／ｃｍ² が適する。そして炭化後
の炭素繊維と樹脂の炭化物及び必要により添加した炭素
微粉とが好ましくは前記した範囲になるように調整す
る。The impregnated sheets are laminated and pressure-molded. 150 to 250 when the impregnating liquid is a thermosetting resin
It is preferable to perform pressure molding while heating to about C. The amount of the impregnating liquid in the sheet is adjusted by the concentration of the impregnating liquid, the immersion conditions, and the pressure applied in the lamination. If the pressure applied is too high, the porosity of the porous carbon plate will decrease, and if it is too low, the adhesion between the resin-impregnated sheets will be impaired, so 0.5-10 kg / cm ² is generally suitable. Then, the carbon fiber after carbonization, the carbide of the resin, and the carbon fine powder added if necessary are preferably adjusted to fall within the above-mentioned range.

【００２１】含浸した樹脂及び有機高分子繊維は炭化に
より重量が減少するので、それらを考慮して含浸量は定
める必要がある。この望ましい例をあげれば有機高分子
繊維６０〜９０重量部、パルプ３〜３５重量部、抄紙用
バインダー２〜２０重量部、これらの合計１００重量部
に対し、炭素微粉０〜１８重量部のシートに熱硬化性樹
脂を含浸する場合はシート１００重量部に対し、樹脂６
０〜１５０重量部（溶剤等を除く樹脂固形分）である。
これによって炭素繊維４０〜６５重量％、樹脂の炭化物
３５〜６０％、炭素微粉０〜１５％の電極が得られる。
シートの積層はシートが０．４〜０．６ｍｍの厚みの場
合、多孔質電極板の厚さが例えば７〜１１ｍｍのもので
は３０〜４０枚程度積層すればよい。Since the weight of the impregnated resin and the organic polymer fiber is reduced by carbonization, it is necessary to determine the impregnation amount in consideration of them. A desirable example of this is a sheet of carbon fine powder of 60 to 90 parts by weight, pulp of 3 to 35 parts by weight, papermaking binder of 2 to 20 parts by weight, and a total of 100 parts by weight of carbon fine powder of 0 to 18 parts by weight. When the thermosetting resin is impregnated into the resin, resin 6
0 to 150 parts by weight (resin solid content excluding solvent etc.).
As a result, an electrode having 40 to 65% by weight of carbon fiber, 35 to 60% of carbide of resin, and 0 to 15% of fine carbon powder can be obtained.
When the sheets have a thickness of 0.4 to 0.6 mm, about 30 to 40 sheets may be laminated if the thickness of the porous electrode plate is, for example, 7 to 11 mm.

【００２２】積層したシートは加熱して炭化されるが、
有機高分子繊維がＰＡＮ系、ピッチ系等の加熱により溶
融する繊維の場合は炭化の前に不融化処理が必要であ
る。不融化処理は公知の方法に従って通常空気中で２０
０〜３００℃の温度に加熱することにより行なわれる。
この処理は炭化の前であれば有機高分子物質の含浸及び
積層の前後を問わずどの段階でも行なうことができる。
レーヨン、パルプ等のセルロース系繊維、フェノール樹
脂繊維等の溶融しない繊維は不融化処理は必要ない。The laminated sheets are heated and carbonized,
When the organic polymer fiber is a PAN-based fiber, a pitch-based fiber that is melted by heating, infusibilization treatment is required before carbonization. The infusibilization treatment is usually performed in air according to a known method.
It is carried out by heating to a temperature of 0 to 300 ° C.
This treatment can be performed at any stage before or after carbonization, whether before or after the impregnation and lamination of the organic polymer substance.
Cellulose fibers such as rayon and pulp, and non-melting fibers such as phenol resin fibers do not need to be infusibilized.

【００２３】積層したシートは最後に高温に加熱して炭
化されるが、反り防止及び昇温時に発生する温度分布に
起因する反り、ヒビ等を防止するため、黒鉛板等で挾持
し、常法により不活性雰囲気中で焼成炭化される。低温
域での昇温速度が速いとヒビ等が発生し易く、多孔質炭
素板の物性低下を引き起こす。炭化がほぼ完了する６０
０℃までの温度域では３０℃／ｈｒ以下の昇温速度が好
ましい。また多孔質炭素板の電気比抵抗、強度等所望の
物性を得るには９００℃以上に焼成、さらには黒鉛化す
るのが望ましい。黒鉛化の温度は不活性雰囲気中で２，
０００〜２，８００℃が好ましい。温度がこれより低い
と炭素電極の電気抵抗が高く、また高過ぎると電極にヒ
ビ割れが発生する恐れがある。The laminated sheets are finally heated to a high temperature to be carbonized, but in order to prevent warpage and warpage and cracks due to the temperature distribution generated at the time of temperature rise, they are sandwiched with a graphite plate or the like and subjected to a conventional method. Is carbonized by firing in an inert atmosphere. If the rate of temperature rise in the low temperature range is high, cracks and the like are likely to occur, causing deterioration of the physical properties of the porous carbon plate. Carbonization is almost complete 60
In the temperature range up to 0 ° C, a temperature rising rate of 30 ° C / hr or less is preferable. Further, in order to obtain desired physical properties such as electric resistivity and strength of the porous carbon plate, it is desirable that the porous carbon plate be fired at 900 ° C. or higher and further graphitized. Graphitization temperature is 2 in an inert atmosphere.
000-2,800 degreeC is preferable. If the temperature is lower than this, the electric resistance of the carbon electrode is high, and if it is too high, the electrode may be cracked.

【００２４】[0024]

【実施例】以下実施例により具体的に説明する。 １）混合抄紙シートの作製 （シートＡの作製条件）繊維長８ｍｍ、太さ１５デニー
ルのレーヨン繊維７５重量部、繊維長５ｍｍ、太さ２デ
ニールのアクリル繊維７重量部とカナディアン・フリー
ネス６５０ｍｌに叩解した木材パルプ（ＮＢＫＰ：クロ
フトン）１５重量部ならびに繊維状バインダーとしてＰ
ＶＡ繊維（クラレ（株）製，ＶＰＢ１０５，１デニール
×４ｍｍ）を３重量部の割合で混合分散した。次いで湿
潤紙力剤としてエポキシ系樹脂（商品名：エピノックス
ｐ−２０１，ディックハーキュレス社製）を繊維に対し
て０．４ｗｔ％（固形分）添加し、２．５ｗｔ％（水９
７．５ｗｔ％）のスラリーとした。このスラリーをさら
に水で希釈し抄紙濃度０．０５％にて短網型傾斜ワイヤ
ーマシンを用いて抄紙速度３０ｍ／ｍｉｎで抄紙した。
得られたシートは紙幅１ｍ、米坪量１００．０ｇ／ｍ
² 、厚み０．５０ｍｍで地合いのよい、均一でかさ高な
シートであった。Embodiments will be specifically described below with reference to embodiments. 1) Preparation of mixed papermaking sheet (Preparation conditions for sheet A) 75 parts by weight of rayon fiber having a fiber length of 8 mm and a thickness of 15 denier, 7 parts by weight of acrylic fiber having a fiber length of 5 mm and a thickness of 2 denier, and beaten to 650 ml of Canadian freeness. Wood pulp (NBKP: Crofton) 15 parts by weight and P as a fibrous binder
VA fiber (VPB105, 1 denier × 4 mm, manufactured by Kuraray Co., Ltd.) was mixed and dispersed at a ratio of 3 parts by weight. Next, 0.4 wt% (solid content) of epoxy resin (trade name: Epinox p-201, manufactured by Dick Hercules) as a wet paper strength agent was added to the fiber, and 2.5 wt% (water 9
7.5 wt%) of the slurry. The slurry was further diluted with water and papermaking was carried out at a papermaking speed of 30 m / min using a short-netted slanting wire machine at a papermaking concentration of 0.05%.
The obtained sheet has a paper width of 1 m and a rice basis weight of 100.0 g / m.
^{2. The} sheet was uniform and bulky with a thickness of 0.50 mm and good texture.

【００２５】（シートＢの作製条件）繊維長５ｍｍ、太
さ１８デニールのレーヨン繊維７１重量部、カナディア
ン・フリーネス６５０ｍｌに叩解した木材パルプ（ＮＢ
ＫＰ：クロフトン）２０重量部、人造黒鉛粉末（昭和電
工（株）製，ＵＦＧ−３０）４重量部、ＰＶＡ繊維（ク
ラレ（株）製，ＶＰＢ１０５，１デニール×４ｍｍ）５
重量部の割合で混合分散し、シートＡと同条件で抄紙し
た。得られたシートは紙幅１ｍ、米坪量１０５．０ｇ／
ｍ² 、厚み０．５５ｍｍのかさ高で均一なシートであっ
た。(Production conditions for sheet B) 71 parts by weight of rayon fiber having a fiber length of 5 mm and a thickness of 18 denier, wood pulp beaten to 650 ml of Canadian freeness (NB
KP: Crofton) 20 parts by weight, artificial graphite powder (Showa Denko KK, UFG-30) 4 parts by weight, PVA fiber (Kuraray VPB105, 1 denier x 4 mm) 5
The mixture was mixed and dispersed at a ratio of parts by weight, and paper was made under the same conditions as the sheet A. The obtained sheet has a paper width of 1 m and a rice basis weight of 105.0 g /
It was a bulky and uniform sheet having m ² and a thickness of 0.55 mm.

【００２６】２）樹脂含浸、加圧・加熱成形 上記・混合抄紙シートをフェノール樹脂（昭和高分子
（株）製，ＢＲＬ−１２０Ｚ）に浸漬し、引き上げてか
ら積層、加熱・加圧成形し、グリーン成形板とした。な
お、フェノール樹脂は人造黒鉛粉末を添加したものとし
ないものを使用した。樹脂の含浸量はフェノール樹脂溶
液に水を加え、樹脂の濃度を調整することにより行なっ
た。樹脂を含浸したシートは取扱いを容易とするため、
先ず１２０℃で２分間予備乾燥し、次いで５００ｍｍ角
に切断しこれを４０枚積層した。積層体を２００℃、圧
力を０．５〜１０ｋｇ／ｃｍ² の範囲で調整し、グリー
ン成形板のかさ密度を０．６５ｇ／ｃｍ³ とした。2) Resin impregnation, pressure / heat molding The above-mentioned mixed papermaking sheet is dipped in a phenol resin (BRL-120Z manufactured by Showa Highpolymer Co., Ltd.), pulled up, and then laminated, heat / pressure molded, It was a green molded plate. The phenolic resin used was one with or without the addition of artificial graphite powder. The resin impregnation amount was determined by adding water to the phenol resin solution to adjust the resin concentration. Since the resin-impregnated sheet is easy to handle,
First, it was pre-dried at 120 ° C. for 2 minutes, then cut into 500 mm square pieces and 40 sheets were laminated. The laminate was adjusted to 200 ° C., the pressure was adjusted to 0.5 to 10 kg / cm ² , and the green molded plate had a bulk density of 0.65 g / cm ³ .

【００２７】このグリーン成形板の樹脂含浸量を表１に
示す。Table 1 shows the resin impregnation amount of this green molded plate.

【表１】 （＊）樹脂固形分換算・含浸量 （Ｘ）含浸液のフェノール樹脂に対し人造黒鉛粉（昭和
電工（株）製，ＵＦＧ−３０，平均粒径１０μｍ）を１
５重量％混合して含浸した。 （Ｙ）含浸液のフェノール樹脂に対し人造黒鉛粉（昭和
電工（株）製，ＵＦＧ−３０，平均粒径１０μｍ）を２
０重量％混合して含浸した。[Table 1] (*) Resin solid content conversion / impregnation amount (X) 1 part of artificial graphite powder (UFG-30, Showa Denko KK, average particle size 10 μm) was added to the phenol resin of the impregnation liquid.
5 wt% was mixed and impregnated. (Y) Artificial graphite powder (UFG-30, Showa Denko KK, average particle size 10 μm) was added to 2 parts of the phenol resin of the impregnating liquid.
The mixture was impregnated with 0% by weight.

【００２８】このグリーン成形板を黒鉛板に挾持し、パ
ッキングコークス中に埋めて１，０００℃／４８時間で
焼成炭化した。さらに焼成後アチソン型黒鉛化炉で２，
３００℃／１０時間にして黒鉛化した。得られた多孔質
炭素板は１８％の寸法収縮、約４０％の厚み収縮を示し
たがサイズは約４１０ｍｍ角、厚み約１０ｍｍの全て外
観良好な炭素板であった。This green molded plate was held between graphite plates, embedded in packing coke, and carbonized by firing at 1,000 ° C./48 hours. After firing, in an Acheson type graphitization furnace
Graphitization was carried out at 300 ° C./10 hours. The obtained porous carbon plate showed a dimensional shrinkage of 18% and a thickness shrinkage of about 40%, but the size was about 410 mm square and the thickness was about 10 mm.

【００２９】３）炭素板の物性測定結果3) Measurement results of physical properties of carbon plate

【表２】 [Table 2]

【００３０】４）水処理における殺菌試験（１） 前記のＮｏ．１〜８及び比較例の多孔質炭素板（電極）
を用い、図１に示す電解処理槽を組立て、図２の方法で
空調用冷却水の殺菌テストを行なった。炭素板は直径７
８ｍｍの円板で、スペーサーと組にして１０組積層し
た。試験の結果を表３に示す。4) Sterilization test in water treatment (1) No. Porous carbon plate (electrode) of 1 to 8 and comparative example
Was used to assemble the electrolytic treatment tank shown in FIG. 1 and a sterilization test of cooling water for air conditioning was conducted by the method shown in FIG. Carbon plate has a diameter of 7
Ten pairs of 8-mm discs and spacers were laminated. The test results are shown in Table 3.

【００３１】[0031]

【表３】 [Table 3]

【００３２】５）水処理における殺菌試験（２） Ｎｏ．８の炭素板について図３の方法により長期間の殺
菌試験を行なった。図で１０は空調器冷却水用冷水塔
で、その冷却水を循環水配管１１，１２により空調機器
と連結した。電解処理槽は炭素板直径が２００ｍｍであ
ること以外は試験（１）と同じである。試験における電
解処理槽の液流量は１ｍ³ ／ｈｒ、印加直流電圧は７０
Ｖであった。なお、前記の比較例の炭素電極についても
試験したが、初期から３０日までの間、良い性能を示さ
なかったため３０日で試験を中止した。試験結果を表４
に示す。5) Sterilization test in water treatment (2) No. The carbon plate of No. 8 was subjected to a long-term sterilization test by the method shown in FIG. In the figure, 10 is a cold water tower for cooling water of an air conditioner, and the cooling water is connected to air conditioning equipment by circulating water pipes 11 and 12. The electrolytic treatment tank is the same as the test (1) except that the carbon plate diameter is 200 mm. The liquid flow rate in the electrolytic treatment tank in the test was 1 m ³ / hr, and the applied DC voltage was 70.
It was V. The carbon electrode of the comparative example was also tested, but the test was stopped after 30 days because it did not show good performance from the initial stage to 30 days. Table 4 shows the test results
Shown in

【００３３】[0033]

【表４】 [Table 4]

【００３４】６）金メッキ廃液からの金の回収試験 金メッキにおける洗浄水廃液を被処理液とし、前記のＮ
ｏ．１〜８及び比較例の炭素板を用い、殺菌試験（１）
と同じ電解処理槽を用い、図１の方法により金の回収試
験を行なった。試験結果を表５に示す。6) Gold recovery test from gold plating waste liquid The cleaning liquid waste liquid in gold plating was used as the liquid to be treated, and the above N
o. Sterilization test (1) using carbon plates 1 to 8 and the comparative example
A gold recovery test was conducted by the method shown in FIG. The test results are shown in Table 5.

【００３５】[0035]

【表５】 [Table 5]

【００３６】[0036]

【発明の効果】本発明の電気化学的な水処理における電
極は炭素繊維を含有し、これが有機高分子物質の炭化物
で一体に結合されており、気孔率が高いにもかかわらず
強度が大きく、かつ腐食電流は小さい。このことは耐食
性が大きいことを示し、長期間の使用に耐える。また気
孔径も水処理電解に適した大きさのものがシャープに分
布し、また電極は異方性であり、殺菌や金属回収の効果
が大きい。特に炭素繊維としてセルロース系やＰＡＮ系
の炭素繊維を用い、有機高分子物質として熱硬化性樹脂
を使用した場合、繊維及び樹脂の炭化物はガラス状とな
り、強度、腐食電流の特性が最もよく、また電極として
の殺菌や金属の回収効果が大きい。EFFECT OF THE INVENTION The electrode in the electrochemical water treatment of the present invention contains carbon fibers, which are integrally bonded with a carbide of an organic polymer substance, and have high strength despite having a high porosity, And the corrosion current is small. This shows that the corrosion resistance is great, and it can be used for a long period of time. In addition, the pores having a size suitable for water treatment electrolysis are sharply distributed, and the electrodes are anisotropic, so that the effect of sterilization and metal recovery is great. In particular, when cellulose-based or PAN-based carbon fibers are used as the carbon fibers and a thermosetting resin is used as the organic polymer substance, the fibers and the carbides of the resin become glassy and have the best characteristics of strength and corrosion current. The effect of sterilization and metal recovery as an electrode is great.

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

【図１】電気化学的な水処理の一例を示す工程図であ
る。FIG. 1 is a process drawing showing an example of electrochemical water treatment.

【図２】電気化学的な水処理に使用する電解処理槽の一
例を示す概略断面図である。FIG. 2 is a schematic cross-sectional view showing an example of an electrolytic treatment tank used for electrochemical water treatment.

【図３】電気化学的な水処理の他の例を示す工程図であ
る。FIG. 3 is a process drawing showing another example of electrochemical water treatment.

【符号の説明】[Explanation of symbols]

１ 被処理液貯槽 ２ ポンプ ３ フィルター ４ 電解槽 ４１ 筐体 ４２ 電圧印加端子 ４３ ターミナル電極 ４４ スペーサー ４５ 多孔質炭素電極板 ４６ 液の入口 ４７ 液の出口 ５ 直流電源 ６ 弁 ７ 弁 ８ 弁 ９ 弁 １０ 空調器冷却水用冷水塔 １１ 循環水配管（出口） １２ 循環水配管（入口） 1 treated liquid storage tank 2 pump 3 filter 4 electrolysis tank 41 casing 42 voltage application terminal 43 terminal electrode 44 spacer 45 porous carbon electrode plate 46 liquid inlet 47 liquid outlet 5 direct current power supply 6 valves 7 valves 8 valves 9 valves 10 Cooling tower for cooling water for air conditioner 11 Circulating water pipe (outlet) 12 Circulating water pipe (inlet)

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.⁶ 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｃ２５Ｂ 11/12 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location // C25B 11/12

Claims (18)

【特許請求の範囲】[Claims] 【請求項１】 炭素繊維が有機高分子物質の炭化物で一
体に結合されてなる電気化学的な水処理用多孔質炭素電
極。1. A porous carbon electrode for electrochemical water treatment in which carbon fibers are integrally bonded with a carbide of an organic polymer. 【請求項２】 電極の通水方向とこれに直角方向とが異
方性である請求項１に記載の炭素電極。2. The carbon electrode according to claim 1, wherein the water flow direction of the electrode and the direction perpendicular to the water flow direction are anisotropic. 【請求項３】 炭素繊維４０〜６５重量％、有機高分子
物質の炭化物３５〜６５重量％である請求項１又は２に
記載の炭素電極。3. The carbon electrode according to claim 1, which comprises 40 to 65% by weight of carbon fiber and 35 to 65% by weight of a carbide of an organic polymer substance. 【請求項４】 炭素微粉を１５重量％以下含む請求項１
〜３のいずれかに記載の炭素電極。4. The fine carbon powder is contained in an amount of 15% by weight or less.
The carbon electrode according to any one of 1 to 3. 【請求項５】 炭素繊維がセルロース繊維の炭化物であ
る請求項１〜４のいずれかに記載の炭素電極。5. The carbon electrode according to claim 1, wherein the carbon fiber is a carbide of cellulose fiber. 【請求項６】 有機高分子物質が熱硬化性樹脂である請
求項１〜５のいずれかに記載の炭素電極。6. The carbon electrode according to claim 1, wherein the organic polymer substance is a thermosetting resin. 【請求項７】 腐食電流１０μＡｍｐ／ｃｍ² 以下（９
５重量％、２００℃リン酸溶液）、電気比抵抗２０ｍΩ
ｃｍ以下である請求項１〜６のいずれかに記載の炭素電
極。7. A corrosion current of 10 μAmp / cm ² or less (9
5% by weight, 200 ° C. phosphoric acid solution), electrical resistivity 20 mΩ
The carbon electrode according to any one of claims 1 to 6, which has a size of cm or less. 【請求項８】 気孔率が５０％以上、気孔径は８０％以
上が３０〜９０μｍである請求項１〜７のいずれかに記
載の炭素電極。8. The carbon electrode according to claim 1, which has a porosity of 50% or more and a pore diameter of 80% or more of 30 to 90 μm. 【請求項９】 曲げ強さが４０ｋｇ／ｃｍ² 以上である
請求項１〜８のいずれかに記載の炭素電極。9. The carbon electrode according to claim 1, which has a bending strength of 40 kg / cm ² or more. 【請求項１０】 水中の微生物の電気化学的な殺菌用で
ある請求項１〜９のいずれかに記載の炭素電極。10. The carbon electrode according to claim 1, which is for electrochemical sterilization of microorganisms in water. 【請求項１１】 金属イオンを含む水溶液中の金属の電
気化学的な回収用である請求項１〜９のいずれかに記載
の炭素電極。11. The carbon electrode according to claim 1, which is for electrochemical recovery of a metal in an aqueous solution containing metal ions. 【請求項１２】 炭素繊維又は炭化により炭素繊維とな
る有機高分子繊維のシートに有機高分子物質を含浸し、
該シートを積層し、加熱して炭化することを特徴とする
電気化学的な水処理用多孔質炭素電極の製造法。12. A carbon fiber or a sheet of an organic polymer fiber which becomes carbon fiber by carbonization is impregnated with an organic polymer substance,
A method for electrochemically treating a porous carbon electrode for water treatment, comprising laminating the sheets and heating to carbonize the sheets. 【請求項１３】 有機高分子繊維を炭化前に不融化処理
することを含む請求項１２に記載の炭素電極の製造法。13. The method for producing a carbon electrode according to claim 12, which comprises infusibilizing the organic polymer fiber before carbonization. 【請求項１４】 有機高分子物質が液状の熱硬化性樹脂
である請求項１２又は１３に記載の炭素電極の製造法。14. The method for producing a carbon electrode according to claim 12, wherein the organic polymer substance is a liquid thermosetting resin. 【請求項１５】 シートが有機高分子繊維６０〜９０重
量部、パルプ３〜３５重量部、抄紙用バインダー２〜２
０重量部を混合し、抄紙したものである請求項１２〜１
４のいずれかに記載の炭素電極の製造法。15. A sheet comprising 60 to 90 parts by weight of organic polymer fibers, 3 to 35 parts by weight of pulp, and binders 2 to 2 for papermaking.
A paper made by mixing 0 parts by weight of the paper.
4. The method for producing a carbon electrode according to any one of 4 above. 【請求項１６】 炭素微粉を残部１００重量部に対し１
８重量部以下含む請求項１２〜１５のいずれかに記載の
炭素電極の製造法。16. The carbon fine powder is 1 per 100 parts by weight of the rest.
The method for producing a carbon electrode according to any one of claims 12 to 15, containing 8 parts by weight or less. 【請求項１７】 水中の微生物の電気化学的な殺菌用で
ある請求項１２〜１６のいずれかに記載の炭素電極の製
造法。17. The method for producing a carbon electrode according to claim 12, which is for electrochemical sterilization of microorganisms in water. 【請求項１８】 金属イオンを含む水溶液中の金属の電
気化学的回収用である請求項１２〜１６のいずれかに記
載の炭素電極の製造法。18. The method for producing a carbon electrode according to claim 12, which is for electrochemical recovery of a metal in an aqueous solution containing metal ions.