JP7280650B2 - FIXED BED ELECTROLYSIS APPARATUS AND ELECTROLYSIS METHOD - Google Patents

FIXED BED ELECTROLYSIS APPARATUS AND ELECTROLYSIS METHOD Download PDF

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JP7280650B2
JP7280650B2 JP2022504379A JP2022504379A JP7280650B2 JP 7280650 B2 JP7280650 B2 JP 7280650B2 JP 2022504379 A JP2022504379 A JP 2022504379A JP 2022504379 A JP2022504379 A JP 2022504379A JP 7280650 B2 JP7280650 B2 JP 7280650B2
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剛史 近藤
駿介 中村
敏史 東條
真 湯浅
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Description

本発明は、固定床電解処理装置及び電解処理方法に関する。 TECHNICAL FIELD The present invention relates to a fixed bed electrolysis apparatus and an electrolysis method.

導電性ダイヤモンド電極は、白金電極等と比較して電位窓が広く、効率的にＯＨラジカル、オゾン等の活性種を生成することが可能であり、耐食性にも優れていることから、例えば、工場排水等の被処理水を電解処理する際の電解用電極としての応用が期待されている。 Conductive diamond electrodes have a wider potential window than platinum electrodes, etc., can efficiently generate active species such as OH radicals and ozone, and have excellent corrosion resistance. It is expected to be applied as an electrode for electrolysis when electrolyzing water to be treated such as wastewater.

導電性ダイヤモンドは、一般に、化学気相成長法（ＣＶＤ法）により、シリコンウェハ等の基板上に成膜される。このため、電極の形状が薄膜状に限定されてしまうという課題があった。また、得られる導電性ダイヤモンド薄膜の面積はＣＶＤ装置のサイズに依存するため、電極表面積を拡大することが困難であるという課題があった。 Conductive diamond is generally deposited on a substrate such as a silicon wafer by chemical vapor deposition (CVD). Therefore, there is a problem that the shape of the electrode is limited to a thin film. Moreover, since the area of the conductive diamond thin film to be obtained depends on the size of the CVD apparatus, there is a problem that it is difficult to increase the electrode surface area.

これらの課題を解決するため、近年、導電性ダイヤモンド粒子を電極に応用することが提案されている。このような導電性ダイヤモンド粒子によれば、電極の形状が薄膜状に限定されないことに加え、電極表面積を容易に拡大することができる。 In order to solve these problems, it has recently been proposed to apply conductive diamond particles to electrodes. According to such conductive diamond particles, the shape of the electrode is not limited to a thin film, and the surface area of the electrode can be easily increased.

例えば、特許文献１には、導電性ダイヤモンド粒子を流動床電極として用いた流動床電解処理装置が開示されている。 For example, Patent Literature 1 discloses a fluidized bed electrolysis apparatus using conductive diamond particles as a fluidized bed electrode.

特開２００８－３６６３１号公報JP-A-2008-36631

特許文献１に記載の流動床電解処理装置では、導電性ダイヤモンド粒子がバイポーラ電極として振る舞うことにより、粒子が浮遊状態であっても電解が起こるものと考えられる。このため、被処理水の導電率が高い場合には、電解効率が低下すると予想される。 In the fluidized bed electrolysis apparatus described in Patent Document 1, electrolysis is thought to occur even when the particles are in a floating state because the conductive diamond particles behave as bipolar electrodes. Therefore, when the conductivity of the water to be treated is high, the electrolysis efficiency is expected to decrease.

本発明は、導電率が高い被処理水であっても電気化学的に処理可能な固定床電解処理装置、及びこの固定床電解処理装置を用いた電解処理方法を提供することを課題とする。 An object of the present invention is to provide a fixed bed electrolysis apparatus capable of electrochemically treating water to be treated even with high conductivity, and an electrolysis method using this fixed bed electrolysis apparatus.

上記課題を解決するための具体的な手段には、以下の実施態様が含まれる。
＜１＞ 被処理水を電気化学的に処理する固定床電解処理装置であって、
導電性ダイヤモンド粒子の充填層を有する、陽極としての固定床電極と、
陰極としての対電極と、
前記固定床電極及び前記対電極が配置されるとともに、前記被処理水が通液される流路を有する電解槽と、
を備え、
前記導電性ダイヤモンド粒子が、ダイヤモンドからなる粒子状基材の表面に導電性ダイヤモンド層が形成されたものであり、
前記固定床電極が前記流路の上流側に配置され、且つ、前記対電極が前記流路の下流側に配置されるか、又は、前記固定床電極が前記流路の下流側に配置され、且つ、前記対電極が前記流路の上流側に配置され、
前記充填層が、前記流路の断面全体に亘って設けられる固定床電解処理装置。
＜２＞ 前記導電性ダイヤモンド層がボロンドープダイヤモンド層である＜１＞に記載の固定床電解処理装置。
＜３＞ 前記固定床電極が、前記導電性ダイヤモンド粒子の充填層に電気的に接続した集電体を有する＜１＞又は＜２＞に記載の固定床電解処理装置。
＜４＞ 前記固定床電極が前記流路の上流側に配置され、且つ、前記対電極が前記流路の下流側に配置される＜１＞～＜３＞のいずれか１項に記載の固定床電解処理装置。
＜５＞ ＜１＞～＜４＞のいずれか１項に記載の固定床電解処理装置の流路に被処理水を通液しながら電極間に電圧を印加することにより、前記被処理水を電気化学的に且つ連続的に処理する電解処理方法。 Specific means for solving the above problems include the following embodiments.
<1> A fixed-bed electrolytic treatment apparatus for electrochemically treating water to be treated,
a fixed bed electrode as an anode, having a packed bed of conductive diamond particles;
a counter electrode as a cathode ;
an electrolytic cell in which the fixed bed electrode and the counter electrode are arranged and which has a channel through which the water to be treated flows;
with
The conductive diamond particles are obtained by forming a conductive diamond layer on the surface of a particulate substrate made of diamond,
The fixed bed electrode is arranged upstream of the channel and the counter electrode is arranged downstream of the channel, or the fixed bed electrode is arranged downstream of the channel, and the counter electrode is arranged upstream of the channel,
A fixed-bed electrolysis apparatus in which the packed bed is provided over the entire cross section of the channel .
<2> The fixed bed electrolysis apparatus according to <1>, wherein the conductive diamond layer is a boron-doped diamond layer .
<3> The fixed bed electrolytic treatment apparatus according to <1> or <2>, wherein the fixed bed electrode has a current collector electrically connected to the packed layer of the conductive diamond particles .
<4> The fixation according to any one of <1> to <3> , wherein the fixed bed electrode is arranged upstream of the flow channel, and the counter electrode is arranged downstream of the flow channel. Floor electrolysis device .
<5> By applying a voltage between the electrodes while the water to be treated flows through the flow path of the fixed bed electrolysis apparatus according to any one of <1> to <4> , the water to be treated is Electrolytic processing method for electrochemically and continuously processing .

本発明によれば、導電率が高い被処理水であっても電気化学的に処理可能な固定床電解処理装置、及びこの固定床電解処理装置を用いた電解処理方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the fixed-bed electrolysis apparatus which can electrochemically process even the to-be-processed water with high electrical conductivity, and the electrolysis method using this fixed-bed electrolysis apparatus can be provided.

本実施形態に係る固定床電解処理装置の一例を示す図である。It is a figure which shows an example of the fixed-bed electrolysis apparatus which concerns on this embodiment. 本実施形態に係る固定床電解処理装置の他の例を示す図である。It is a figure which shows the other example of the fixed-bed electrolysis apparatus which concerns on this embodiment. 試験例１で得られたサイクリックボルタモグラムを示す図である。4 is a diagram showing a cyclic voltammogram obtained in Test Example 1. FIG. 試験例２において、被処理水として５０μＭ メチレンブルー水溶液を用いて３Ｖ、４Ｖ、又は５Ｖで定電圧電解を行った際の、６０分後におけるメチレンブルー濃度の減少量を示す図である。FIG. 10 is a diagram showing the amount of decrease in methylene blue concentration after 60 minutes when constant voltage electrolysis was performed at 3 V, 4 V, or 5 V using a 50 μM methylene blue aqueous solution as water to be treated in Test Example 2. FIG. 試験例２において、被処理水として５０μＭ メチレンブルー水溶液を用いて５Ｖで定電圧電解を行った際の、メチレンブルー濃度の時間変化を示す図である。FIG. 10 is a graph showing changes in methylene blue concentration over time when constant voltage electrolysis is performed at 5 V using a 50 μM methylene blue aqueous solution as water to be treated in Test Example 2; 試験例３で用いたバッチ式の固定床電解処理装置の概略構成を示す図である。2 is a diagram showing a schematic configuration of a batch-type fixed-bed electrolysis apparatus used in Test Example 3. FIG. 図６の固定床電解処理装置の電解槽に１ｍＭ テレフタル酸二ナトリウム（ＮａＴＡ）溶液を５ｍＬ加え、５Ｖ、３０分間の定電圧電解を行った後の、溶液の蛍光スペクトルを示す図である。FIG. 7 shows the fluorescence spectrum of the solution after adding 5 mL of 1 mM disodium terephthalate (NaTA) solution to the electrolytic cell of the fixed bed electrolysis apparatus of FIG. 6 and performing constant voltage electrolysis at 5 V for 30 minutes. 図６の固定床電解処理装置の電解槽に１ｍＭ テレフタル酸二ナトリウム（ＮａＴＡ）溶液を５ｍＬ加え、５Ｖ、３０分間の定電圧電解を行った後の、溶液中の２－ヒドロキシテレフタル酸（ＨＴＡ）濃度を示す図である。5 mL of 1 mM disodium terephthalate (NaTA) solution was added to the electrolytic cell of the fixed-bed electrolysis apparatus in FIG. FIG. 4 is a diagram showing concentrations; 試験例４で用いたフロー式の固定床電解処理装置の概略構成を示す図である。FIG. 3 is a diagram showing a schematic configuration of a flow-type fixed-bed electrolysis apparatus used in Test Example 4; 試験例４において、被処理水として５０μＭ メチレンブルー水溶液を用い、流速を２．０ｍＬ／ｍｉｎとして５Ｖで定電圧電解を行った際の、メチレンブルー濃度の時間変化を示す図である。In Test Example 4, a 50 μM methylene blue aqueous solution was used as the water to be treated, and constant voltage electrolysis was performed at a flow rate of 2.0 mL/min and 5 V to show changes over time in methylene blue concentration. 試験例４において、被処理水として５０μＭ メチレンブルー水溶液を用い、流速を０．５ｍＬ／ｍｉｎ又は２．０ｍＬ／ｍｉｎとして５Ｖで定電圧電解を行った際の、メチレンブルー濃度の時間変化を示す図である。In Test Example 4, a 50 μM methylene blue aqueous solution was used as the water to be treated, and constant voltage electrolysis was performed at 5 V at a flow rate of 0.5 mL/min or 2.0 mL/min. FIG. .

以下、本発明を適用した具体的な実施形態について、図面を参照しながら詳細に説明する。 Hereinafter, specific embodiments to which the present invention is applied will be described in detail with reference to the drawings.

本実施形態に係る固定床電解処理装置は、被処理水を電気化学的に処理する固定床電解処理装置であって、導電性ダイヤモンド粒子の充填層を有する固定床電極と、対電極と、固定床電極及び対電極が配置されるとともに、被処理水が収容又は通液される電解槽と、を備える。この固定床電解処理装置の電極間に電圧を印加することにより、被処理水を電気化学的に処理することが可能である。 The fixed-bed electrolysis apparatus according to the present embodiment is a fixed-bed electrolysis apparatus for electrochemically treating water to be treated, comprising a fixed-bed electrode having a packed layer of conductive diamond particles, a counter electrode, a fixed an electrolytic cell in which a floor electrode and a counter electrode are arranged and water to be treated is contained or passed through; Water to be treated can be electrochemically treated by applying a voltage between the electrodes of this fixed-bed electrolytic treatment apparatus.

以下では、まず、導電性ダイヤモンド粒子について説明し、次いで、固定床電解処理装置の構成について説明する。 In the following, the conductive diamond particles will be described first, and then the configuration of the fixed bed electrolytic treatment apparatus will be described.

（導電性ダイヤモンド粒子）
導電性ダイヤモンドとしては、ダイヤモンドに１３族又は１５族の元素をドープして導電性を付与したものが挙げられる。導電性ダイヤモンド粒子の導電率は、例えば、０．０１Ｓ／ｃｍ以上である。１３族又は１５族の元素としては、ホウ素、窒素、リン等が挙げられる。(Conductive diamond particles)
Examples of conductive diamond include those obtained by doping diamond with a Group 13 or Group 15 element to impart conductivity. The conductivity of the conductive diamond particles is, for example, 0.01 S/cm or more. Elements of Group 13 or Group 15 include boron, nitrogen, phosphorus and the like.

導電性ダイヤモンド粒子の形状は特に制限されない。導電性ダイヤモンド粒子の形状は、アスペクト比が１付近の球状、立方体状、又は多面体状であってもよく、アスペクト比が１を上回る形状であってもよい。 The shape of the conductive diamond particles is not particularly limited. The shape of the conductive diamond particles may be spherical, cubic, or polyhedral with an aspect ratio of about 1, or a shape with an aspect ratio of more than 1.

導電性ダイヤモンド粒子の粒子径は、例えば、１μｍ～１０００μｍであることが好ましく、２０μｍ～１００μｍであることがより好ましい。 The particle size of the conductive diamond particles is, for example, preferably 1 μm to 1000 μm, more preferably 20 μm to 100 μm.

導電性ダイヤモンド粒子の中でも、ホウ素がドープされたボロンドープダイヤモンド粒子（ＢＤＤＰ）が好ましい。 Among conductive diamond particles, boron-doped diamond particles (BDDP) are preferred.

ＢＤＤＰの製造方法は特に制限されず、特開２００８－３６６３１号公報、特開２０１８－７６２１６号公報等に記載された公知の製造方法を採用することができる。好ましい製造方法としては、粒子状基材の表面にボロンドープダイヤモンド層（ＢＤＤ層）を形成する方法が挙げられる。以下、この製造方法について説明する。 The method for producing BDDP is not particularly limited, and known production methods described in JP-A-2008-36631, JP-A-2018-76216, etc. can be employed. A preferred manufacturing method includes a method of forming a boron-doped diamond layer (BDD layer) on the surface of a particulate base material. This manufacturing method will be described below.

粒子状基材としては、ＢＤＤ層の形成時に溶融又は変形するものでなければ特に制限されず、目的に応じて適宜選択することができる。粒子状基材の具体例としては、天然又は人工のダイヤモンド粒子；シリコン粒子；モリブデン粒子等の金属粒子；アルミナ粒子等の金属酸化物粒子；窒化ホウ素粒子、石英粒子；などが挙げられる。これらの粒子状基材は、１種類を単独で使用してもよく、２種類以上を併用してもよい。これらの中でも、天然又は人工のダイヤモンド粒子が好ましい。 The particulate base material is not particularly limited as long as it melts or deforms during the formation of the BDD layer, and can be appropriately selected according to the purpose. Specific examples of particulate substrates include natural or artificial diamond particles; silicon particles; metal particles such as molybdenum particles; metal oxide particles such as alumina particles; These particulate base materials may be used singly or in combination of two or more. Among these, natural or artificial diamond particles are preferred.

ＢＤＤ層の形成方法は特に制限されず、目的に応じて適宜選択することができる。形成方法の具体例としては、熱ＣＶＤ法、プラズマＣＶＤ法、熱フィラメントＣＶＤ法等のＣＶＤ法；イオンビーム法、イオン化蒸着法等の物理蒸着法（ＰＶＤ法）；高温高圧法；などが挙げられる。これらの中でも、プラズマＣＶＤ法が好ましい。 A method for forming the BDD layer is not particularly limited, and can be appropriately selected depending on the purpose. Specific examples of the formation method include CVD methods such as thermal CVD, plasma CVD, and hot filament CVD; physical vapor deposition (PVD) such as ion beam and ionization; high temperature and high pressure; . Among these, the plasma CVD method is preferred.

上述したＣＶＤ法において、ＢＤＤ層の原料となる炭素源及びホウ素源は特に制限されない。炭素源としては、メタン、アセトン等を用いることができる。また、ホウ素源としては、ジボラン、トリメチルボラン、トリメトキシボラン等を用いることができる。 In the above-described CVD method, the carbon source and boron source, which are raw materials for the BDD layer, are not particularly limited. Methane, acetone, etc. can be used as the carbon source. Moreover, diborane, trimethylborane, trimethoxyborane, etc. can be used as a boron source.

ＢＤＤ層において、ダイヤモンドにドープするホウ素の量は、ダイヤモンドを構成する炭素に対して、１０ｐｐｍ以上であることが好ましく、１０００ｐｐｍ以上であることがより好ましく、１００００ｐｐｍ以上であることがさらに好ましい。ダイヤモンドにドープするホウ素の量は、二次イオン質量分析法等により測定することができる。 In the BDD layer, the amount of boron with which diamond is doped is preferably 10 ppm or more, more preferably 1000 ppm or more, and even more preferably 10000 ppm or more, relative to the carbon constituting the diamond. The amount of boron with which diamond is doped can be measured by secondary ion mass spectrometry or the like.

（固定床電解処理装置の一例）
固定床電解処理装置の一例を図１に示す。図１に示す固定床電解処理装置１は、固定床電極（陽極）１０と、対電極（陰極）２０と、固定床電極１０及び対電極２０が配置されるとともに、被処理水が収容される電解槽３０と、を備える。図１に示す固定床電解処理装置１は、電解槽３０に収容された被処理水を電解処理するバッチ式の固定床電解処理装置の一例である。(An example of a fixed-bed electrolysis apparatus)
An example of a fixed bed electrolysis apparatus is shown in FIG. A fixed-bed electrolysis apparatus 1 shown in FIG. 1 includes a fixed-bed electrode (anode) 10, a counter electrode (cathode) 20, and a fixed-bed electrode 10 and a counter electrode 20, and contains water to be treated. and an electrolytic bath 30 . A fixed-bed electrolysis apparatus 1 shown in FIG. 1 is an example of a batch-type fixed-bed electrolysis apparatus that electrolyzes water to be treated contained in an electrolytic bath 30 .

固定床電極１０は、上述した導電性ダイヤモンド粒子が充填されてなる充填層１１と、該充填層１１と電気的に接続された集電体１２と、を有する。集電体１２の材質としては、銅、アルミニウム等の金属；導電性ダイヤモンド；などが挙げられる。集電体１２は、リードと一体に形成されたものであってもよい。 The fixed bed electrode 10 has a filling layer 11 filled with the above-described conductive diamond particles and a current collector 12 electrically connected to the filling layer 11 . Examples of the material of the current collector 12 include metals such as copper and aluminum; conductive diamond; and the like. The current collector 12 may be formed integrally with the lead.

対電極２０は、固定床電極１０とともに電解用電極を構成する。対電極２０としては、白金電極、金電極、ステンレス電極、導電性ダイヤモンド電極等が挙げられる。対電極２０は、導電性ダイヤモンド粒子の充填層を有する固定床電極であってもよい。 The counter electrode 20 constitutes an electrode for electrolysis together with the fixed bed electrode 10 . Examples of the counter electrode 20 include a platinum electrode, a gold electrode, a stainless electrode, a conductive diamond electrode, and the like. The counter electrode 20 may be a fixed bed electrode with a packed bed of conductive diamond particles.

電解槽３０は、上述した固定床電極１０及び対電極２０が配置されるとともに、被処理水が収容される。電解槽３０には、被処理水を撹拌する撹拌子が設けられていてもよい。 The electrolytic cell 30 is provided with the above-described fixed bed electrode 10 and counter electrode 20, and contains water to be treated. The electrolytic bath 30 may be provided with a stirrer for stirring the water to be treated.

以上説明した固定床電解処理装置１によれば、固定床電極１０と対電極２０との間に電圧を印加することにより、電解槽３０に収容された被処理水を電解処理することができる。導電性ダイヤモンドを用いた電極は、電位窓が広く、水の電気分解が抑えられ、有機物等の電解反応が進行し易くなることが知られている。したがって、例えば、被処理水が有機物を含有する場合には、電圧印加によって発生したＯＨラジカル、オゾン等の活性種により、有機物を効率的に分解することができる。しかも、本実施形態では、導電性ダイヤモンド粒子を固定床電極として配置するため、電極表面積が拡大し、電解効率の向上を図ることができる。また、被処理水が金属イオンを含有する場合には、電圧印加により金属イオンを還元し、金属を回収することができる。 According to the fixed bed electrolysis apparatus 1 described above, by applying a voltage between the fixed bed electrode 10 and the counter electrode 20, the water to be treated contained in the electrolytic bath 30 can be electrolyzed. It is known that an electrode using conductive diamond has a wide potential window, suppresses the electrolysis of water, and facilitates the progress of electrolysis reactions of organic substances and the like. Therefore, for example, when the water to be treated contains organic matter, the organic matter can be efficiently decomposed by active species such as OH radicals and ozone generated by voltage application. Moreover, in this embodiment, since the conductive diamond particles are arranged as the fixed-bed electrode, the surface area of the electrode is increased, and the electrolysis efficiency can be improved. Moreover, when the water to be treated contains metal ions, the metal ions can be reduced by applying a voltage to recover the metal.

被処理水を電解処理する際の電圧及びその印加時間は特に制限されず、被処理水の種類等に応じて適宜選択することができる。 The voltage and its application time when the water to be treated is electrolytically treated are not particularly limited, and can be appropriately selected according to the type of the water to be treated.

（固定床電解処理装置の他の例）
固定床電解処理装置の他の例を図２に示す。図２に示す固定床電解処理装置２は、電解槽に収容された被処理水を電解処理するのではなく、電解槽に通液された被処理水を連続的に電解処理する点で図１に示す固定床電解処理装置１と異なる。そこで、図１と共通する構成については同一の符号を付し、詳細な説明を省略する。(Another example of fixed bed electrolysis apparatus)
Another example of the fixed bed electrolysis apparatus is shown in FIG. The fixed bed electrolysis apparatus 2 shown in FIG. 2 does not electrolyze the water to be treated contained in the electrolytic cell, but continuously electrolyzes the water to be treated that is passed through the electrolytic cell. 1 is different from the fixed bed electrolysis apparatus 1 shown in FIG. 1 are given the same reference numerals, and detailed description thereof will be omitted.

図２に示す固定床電解処理装置２は、固定床電極（陽極）４０と、対電極（陰極）２０と、固定床電極４０及び対電極２０が配置されるとともに、被処理水が通液される流路を有する電解槽５０と、を備える。図２に示す固定床電解処理装置２は、電解槽５０に通液された被処理水を連続的に電解処理するフロー式の固定床電解処理装置の一例である。 The fixed bed electrolysis apparatus 2 shown in FIG. 2 includes a fixed bed electrode (anode) 40, a counter electrode (cathode) 20, and the fixed bed electrode 40 and the counter electrode 20, and water to be treated is passed. and an electrolytic bath 50 having a flow path. The fixed-bed electrolysis apparatus 2 shown in FIG. 2 is an example of a flow-type fixed-bed electrolysis apparatus that continuously electrolyzes water to be treated that has been passed through an electrolytic bath 50 .

固定床電極４０は、上述した導電性ダイヤモンド粒子が充填されてなり、被処理水が通液される流路の断面全体に亘って設けられた充填層４１と、該充填層４１に挿入された集電体４２と、該充填層４１を挟むように設けられた一対のフィルタ４３ａ，４３ｂと、を有する。集電体４２の材質としては、銅、アルミニウム等の金属；導電性ダイヤモンド；などが挙げられる。フィルタ４３ａ，４３ｂとしては、被処理水を通し、且つ、孔径が導電性ダイヤモンド粒子の粒子径よりも小さいものであれば特に制限されない。 The fixed bed electrode 40 is filled with the above-described conductive diamond particles, and has a filling layer 41 provided over the entire cross section of the flow path through which the water to be treated flows. It has a current collector 42 and a pair of filters 43a and 43b provided so as to sandwich the filling layer 41 therebetween. Materials for the current collector 42 include metals such as copper and aluminum; conductive diamond; and the like. The filters 43a and 43b are not particularly limited as long as the water to be treated passes through them and the pore diameter is smaller than the particle diameter of the conductive diamond particles.

電解槽５０は、被処理水が図中矢印の方向（図中の下側から上側への方向）に通液される流路を有し、上流側に固定床電極４０が配置されるとともに、下流側に対電極２０が配置されている。 The electrolytic cell 50 has a flow path through which the water to be treated flows in the direction of the arrow in the figure (the direction from the bottom to the top in the figure), and the fixed bed electrode 40 is arranged upstream, A counter electrode 20 is arranged downstream.

以上説明した固定床電解処理装置２によれば、固定床電極４０と対電極２０との間に電圧を印加することにより、電解槽５０に通液された被処理水を連続的に電解処理することができる。 According to the fixed bed electrolysis apparatus 2 described above, by applying a voltage between the fixed bed electrode 40 and the counter electrode 20, the water to be treated that has flowed through the electrolytic cell 50 is continuously electrolyzed. be able to.

特に、図２に示す固定床電解処理装置２では、被処理水が通液される流路の断面全体に亘って充填層４１が設けられているため、被処理水が確実に充填層４１を通過することになり、より効率的な電解処理が可能となる。例えば、被処理水が有機物を含有する場合には、電圧印加によって発生したＯＨラジカル等の活性種により、有機物をより効率的に分解することが可能となる。 In particular, in the fixed-bed electrolytic treatment apparatus 2 shown in FIG. 2, since the filling layer 41 is provided over the entire cross section of the flow path through which the water to be treated flows, the water to be treated reliably flows through the filling layer 41. It will pass through, and more efficient electrolytic treatment becomes possible. For example, when the water to be treated contains organic matter, active species such as OH radicals generated by voltage application can more efficiently decompose the organic matter.

被処理水を電解処理する際の電圧及びその印加時間は特に制限されず、被処理水の種類等に応じて適宜選択することができる。 The voltage and its application time when the water to be treated is electrolytically treated are not particularly limited, and can be appropriately selected according to the type of the water to be treated.

なお、図２に示す固定床電解処理装置２では、固定床電極４０が流路の上流側に配置され、対電極２０が流路の下流側に配置されているが、この例に限定されるものではなく、固定床電極４０を流路の下流側に配置し、対電極２０を流路の上流側に配置してもよい。 In the fixed bed electrolysis apparatus 2 shown in FIG. 2, the fixed bed electrode 40 is arranged on the upstream side of the flow channel and the counter electrode 20 is arranged on the downstream side of the flow channel, but it is limited to this example. Alternatively, the fixed bed electrode 40 may be placed downstream of the channel and the counter electrode 20 may be placed upstream of the channel.

また、図２に示す固定床電解処理装置２では、充填層４１が流路の断面全体に亘って設けられているが、この例に限定されるものではなく、流路の断面の少なくとも一部に設けられていればよい。 In addition, in the fixed-bed electrolysis apparatus 2 shown in FIG. 2, the filling layer 41 is provided over the entire cross section of the flow channel, but it is not limited to this example, and at least part of the cross section of the flow channel is provided. It is sufficient if it is provided in

以下、実施例によって本発明をより具体的に説明するが、本発明はこれら実施例によって制限されるものではない。 EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.

＜製造例１：ボロンドープダイヤモンド薄膜（ＢＤＤ薄膜）の製造＞
粒子径が３μｍ～６μｍのダイヤモンド粒子を用いてシリコンウェハの表面に傷付け処理を施した後、メタノール、アセトン、及び超純水を用いて各３０分間、超音波洗浄を行った。次いで、マイクロ波プラズマＣＶＤ法により、シリコンウェハ上にＢＤＤ薄膜を成膜した。成膜条件は、マイクロ波出力：５５００Ｗ、ステージ温度：６９８℃、チャンバー内圧：９０Ｔｏｒｒ、プレナム圧力：７０Ｔｏｒｒ、成膜時間：４時間、ホウ素濃度：１００００ｐｐｍとした。<Production Example 1: Production of boron-doped diamond thin film (BDD thin film)>
After the surface of the silicon wafer was scratched with diamond particles having a particle size of 3 μm to 6 μm, it was ultrasonically cleaned with methanol, acetone, and ultrapure water for 30 minutes each. Then, a BDD thin film was formed on the silicon wafer by microwave plasma CVD. The deposition conditions were microwave output: 5500 W, stage temperature: 698° C., chamber internal pressure: 90 Torr, plenum pressure: 70 Torr, deposition time: 4 hours, boron concentration: 10000 ppm.

＜製造例２：ボロンドープダイヤモンド粒子（ＢＤＤＰ）の製造＞
粒子状基材として、粒子径が４０μｍ～６０μｍのダイヤモンド粒子を用いた。まず、ダイヤモンド粒子に含まれる不純物（Ｃｏ、Ｆｅ、各種ｓｐ２カーボン等）を除去するため、既報に従って洗浄を行った。具体的には、ダイヤモンド粒子を、塩酸と硝酸とを体積比３：１で混合した王水中に浸漬して６０℃で３０分間加熱した後、３０％過酸化水素水中に浸漬して６０℃で３０分間加熱した。その後、超純水、２－プロパノール、及びアセトンを用いて順に洗浄し、加熱炉で乾燥させた。次いで、洗浄後のダイヤモンド粒子を約０．８ｇ秤量し、マイクロ波プラズマＣＶＤ法により、ダイヤモンド粒子の表面にＢＤＤ層を形成してＢＤＤＰを得た。成膜条件は、マイクロ波出力：１３００Ｗ、ステージ温度：８００℃、チャンバー内圧：５０Ｔｏｒｒ、成膜時間：８時間、ホウ素濃度：２００００ｐｐｍとした。<Production Example 2: Production of boron-doped diamond particles (BDDP)>
Diamond particles with a particle size of 40 μm to 60 μm were used as the particulate base material. First, in order to remove impurities (Co, Fe, various types of sp2 carbon, etc.) contained in the diamond particles, cleaning was performed according to the previous report. Specifically, the diamond particles were immersed in aqua regia, which was a mixture of hydrochloric acid and nitric acid at a volume ratio of 3:1, heated at 60°C for 30 minutes, and then immersed in 30% hydrogen peroxide water and heated to 60°C. Heated for 30 minutes. After that, it was washed with ultrapure water, 2-propanol, and acetone in that order, and dried in a heating furnace. Next, about 0.8 g of the washed diamond particles were weighed, and a BDD layer was formed on the surface of the diamond particles by microwave plasma CVD to obtain BDDP. The film formation conditions were microwave output: 1300 W, stage temperature: 800° C., chamber internal pressure: 50 Torr, film formation time: 8 hours, and boron concentration: 20000 ppm.

＜製造例３：固定床電解処理装置の製造＞
製造例１で得たＢＤＤ薄膜（２ｃｍ×２ｃｍ）上に、遠心チューブ（内面積：１ｃｍ２）を長さ１０ｃｍに切断した筒状部品を固定した。その際、液漏れが起きないように、筒状部品とＢＤＤ薄膜との間にＯリング（内面積：１ｃｍ２）を介在させた。次いで、筒状部品の内部に、製造例２で得たＢＤＤＰ（粒子径：４０μｍ～６０μｍ）を所定量だけ充填し、固定床電極（以下、「ＢＤＤＰ充填電極」という。）を構成した。そして、白金線を対電極として、図１に示す構成のバッチ式の固定床電解処理装置を製造した。以下に示す試験例１、２では、このバッチ式の固定床電解処理装置を用いて実験を行った。<Production Example 3: Production of Fixed Bed Electrolytic Treatment Apparatus>
A cylindrical part obtained by cutting a centrifuge tube (inner area: 1 cm 2 ) into a length of 10 cm was fixed on the BDD thin film (2 cm×2 cm) obtained in Production Example 1. At that time, an O-ring (inner area: 1 cm 2 ) was interposed between the cylindrical part and the BDD thin film so as not to cause liquid leakage. Next, a predetermined amount of BDDP (particle size: 40 μm to 60 μm) obtained in Production Example 2 was filled into the cylindrical part to form a fixed bed electrode (hereinafter referred to as “BDDP-filled electrode”). Using a platinum wire as a counter electrode, a batch-type fixed-bed electrolysis apparatus having the configuration shown in FIG. 1 was manufactured. In Test Examples 1 and 2 shown below, experiments were conducted using this batch-type fixed-bed electrolysis apparatus.

＜試験例１：ＢＤＤＰ充填電極の電極表面積の評価＞
ＢＤＤＰ充填電極の電極表面積がＢＤＤ薄膜電極よりも拡大するか、及びＢＤＤＰの充填量を増やすことによりＢＤＤＰ充填電極の電極表面積が拡大するかを確認するため、サイクリックボルタンメトリー（ＣＶ）によりバックグラウンド電流の大きさを比較した。ＣＶ測定は、ＢＤＤＰ充填電極又はＢＤＤ薄膜電極を作用電極、白金線を対電極、Ａｇ／ＡｇＣｌ電極を参照電極とし、０．１Ｍ 硫酸ナトリウム水溶液中で行った。測定電位は－１．３Ｖ～＋１．８Ｖ（ｖｓ． Ａｇ／ＡｇＣｌ）とし、走査速度は１００ｍＶ／ｓｅｃとした。<Test Example 1: Evaluation of electrode surface area of BDDP-filled electrode>
Background current was measured by cyclic voltammetry (CV) to confirm whether the electrode surface area of the BDDP-filled electrode is larger than that of the BDD thin film electrode, and whether increasing the loading of BDDP increases the electrode surface area of the BDDP-filled electrode. compared the size of CV measurement was performed in a 0.1 M sodium sulfate aqueous solution using a BDDP-filled electrode or a BDD thin film electrode as a working electrode, a platinum wire as a counter electrode, and an Ag/AgCl electrode as a reference electrode. The measurement potential was −1.3 V to +1.8 V (vs. Ag/AgCl), and the scanning speed was 100 mV/sec.

ＣＶ測定により得られたサイクリックボルタモグラムを図３に示す。図３に示すとおり、ＢＤＤＰ充填電極を用いた場合のバックグラウンド電流は、ＢＤＤ薄膜電極を用いた場合のバックグラウンド電流よりも大きく、その値はＢＤＤＰの充填量が増えるに従って増大した。このことから、ＢＤＤＰ充填電極の電極表面積はＢＤＤ薄膜電極の電極表面積よりも大きく、また、ＢＤＤＰの充填量を増やすことによりＢＤＤＰ充填電極の電極表面積が拡大することが分かる。 A cyclic voltammogram obtained by CV measurement is shown in FIG. As shown in FIG. 3, the background current with the BDDP-filled electrode was higher than that with the BDD thin film electrode, and the value increased with increasing loading of BDDP. From this, it can be seen that the electrode surface area of the BDDP-filled electrode is larger than the electrode surface area of the BDD thin film electrode, and that the electrode surface area of the BDDP-filled electrode is increased by increasing the filling amount of BDDP.

＜試験例２：バッチ式の固定床電解処理装置を用いたメチレンブルーの定電圧電解実験＞
メチレンブルーを含有する水溶液を被処理水とし、ＢＤＤＰ充填電極又はＢＤＤ薄膜電極による定電圧電解実験を行った。メチレンブルーを用いることで、紫外可視（ＵＶ－ｖｉｓ）吸収スペクトルによる定量が可能となる。<Test Example 2: Constant-voltage electrolysis experiment of methylene blue using a batch-type fixed-bed electrolysis apparatus>
Using an aqueous solution containing methylene blue as water to be treated, a constant voltage electrolysis experiment was conducted using a BDDP-filled electrode or a BDD thin film electrode. The use of methylene blue allows quantification by ultraviolet-visible (UV-vis) absorption spectra.

支持電解質として０．１Ｍ 硫酸ナトリウムを含有する５０μＭ メチレンブルー水溶液を調製し、ＢＤＤＰ充填電極（ＢＤＤＰ充填量：０．２ｇ、０．４ｇ、０．６ｇ、０．８ｇ）又はＢＤＤ薄膜電極（ＢＤＤＰ充填量：０ｇ）を備えた電解処理装置の電解槽に５ｍＬ加えた。その後、６０分間の定電圧電解を行い、メチレンブルー濃度の減少量を定量した。定電圧は３Ｖ、４Ｖ、又は５Ｖとした。メチレンブルー濃度の減少量を定量する際には、メチレンブルー水溶液の上澄み液を採取し、ＵＶ－ｖｉｓ測定を行った。そして、得られた吸光度から、予め作成しておいた検量線によりメチレンブルー濃度に換算した。 A 50 μM methylene blue aqueous solution containing 0.1 M sodium sulfate as a supporting electrolyte was prepared, and a BDDP-filled electrode (BDDP filling amount: 0.2 g, 0.4 g, 0.6 g, 0.8 g) or a BDD thin film electrode (BDDP filling amount : 0 g) was added to the electrolytic cell of the electrolyzer. After that, constant voltage electrolysis was performed for 60 minutes, and the decrease in methylene blue concentration was quantified. The constant voltage was 3V, 4V, or 5V. When quantifying the amount of decrease in methylene blue concentration, the supernatant liquid of the methylene blue aqueous solution was sampled and subjected to UV-vis measurement. Then, the obtained absorbance was converted to methylene blue concentration using a calibration curve prepared in advance.

６０分間の定電圧電解を行った際のメチレンブルー濃度の減少量を図４に示す。図４に示すとおり、印加電圧が大きくなるほど、また、ＢＤＤＰ充填量が増加するほど、メチレンブルー濃度の減少量が増加した。 FIG. 4 shows the amount of decrease in methylene blue concentration when performing constant voltage electrolysis for 60 minutes. As shown in FIG. 4, the amount of decrease in methylene blue concentration increased as the applied voltage increased and as the BDDP filling amount increased.

また、定電圧電解を行った際のメチレンブルー濃度の時間変化を調べるため、５Ｖの定電圧で定電圧電解を行い、１０分ごとに上記と同様にしてメチレンブルー濃度を定量した。なお、測定に用いた上澄み液は、廃液とせずに電解槽内に戻した。 In addition, in order to examine the change in methylene blue concentration over time during constant voltage electrolysis, constant voltage electrolysis was performed at a constant voltage of 5 V, and the methylene blue concentration was quantified every 10 minutes in the same manner as described above. The supernatant liquid used for the measurement was returned to the electrolytic cell without being discharged.

５Ｖの定電圧電解を行った際のメチレンブルー濃度の時間変化を図５に示す。図５は、メチレンブルーの初期濃度を１００％としたときの相対値を表したものである。図５に示すとおり、ＢＤＤＰ充填電極を用いた場合には、電解処理の初期にメチレンブルー濃度が大きく減少し、メチレンブルー濃度が低くなるに従って減少速度が低下した。 FIG. 5 shows the change in methylene blue concentration over time when electrolysis was performed at a constant voltage of 5V. FIG. 5 shows relative values when the initial concentration of methylene blue is 100%. As shown in FIG. 5, when the BDDP-filled electrode was used, the methylene blue concentration decreased greatly at the beginning of the electrolysis treatment, and the decrease rate decreased as the methylene blue concentration decreased.

＜試験例３：バッチ式の固定床電解処理装置によるＯＨラジカル生成の評価＞
試験例３では、図６に示す構成のバッチ式の固定床電解処理装置１Ａを使用して実験を行った。内容積５．５ｍＬの電解槽１０Ａの内部には、製造例２で得たＢＤＤＰ（粒子径：４０μｍ～６０μｍ）を所定量（０ｇ、０．２ｇ、０．４ｇ、０．６ｇ、０．８ｇ）だけ充填して固定床電極（ＢＤＤＰ充填電極）１０Ａの充填層１１Ａを構成した。固定床電極１０Ａの集電体１２Ａ及び対電極２０Ａとしては、白金線を使用した。<Test Example 3: Evaluation of OH Radical Generation by Batch Type Fixed Bed Electrolytic Treatment Apparatus>
In Test Example 3, an experiment was conducted using a batch-type fixed-bed electrolysis apparatus 1A having the configuration shown in FIG. A predetermined amount (0 g, 0.2 g, 0.4 g, 0.6 g, 0.8 g) of BDDP (particle size: 40 μm to 60 μm) obtained in Production Example 2 was placed inside the electrolytic cell 10A having an internal volume of 5.5 mL. ) to form a filling layer 11A of a fixed bed electrode (BDDP filling electrode) 10A. A platinum wire was used as the current collector 12A and the counter electrode 20A of the fixed bed electrode 10A.

１．０ｍＭのテレフタル酸二ナトリウム（ＮａＴＡ）溶液を電解槽に５ｍＬ加え、５Ｖ、３０分間の定電圧電解を行った後、波長４２５ｎｍの蛍光強度を測定することにより、溶液中の２－ヒドロキシテレフタル酸（ＨＴＡ）の濃度を測定した。電解処理により生じたＯＨラジカルによりＮａＴＡがＨＴＡへと変換されるため、ＨＴＡの濃度を測定することにより、ＯＨラジカルの生成量を間接的に評価することができる。 5 mL of a 1.0 mM disodium terephthalate (NaTA) solution was added to the electrolytic cell, and electrolysis was performed at a constant voltage of 5 V for 30 minutes. Acid (HTA) concentrations were measured. Since NaTA is converted to HTA by OH radicals generated by electrolytic treatment, the amount of OH radicals generated can be indirectly evaluated by measuring the concentration of HTA.

定電圧電解後の溶液の蛍光スペクトルを図７Ａに示し、ＨＴＡ濃度を図７Ｂに示す。図７Ａ及び図７Ｂに示すとおり、ＢＤＤＰ充填量が増加するほどＨＴＡ濃度が上昇しており、ＯＨ生成量が増加したことが分かる。 The fluorescence spectrum of the solution after constant voltage electrolysis is shown in FIG. 7A, and the HTA concentration is shown in FIG. 7B. As shown in FIGS. 7A and 7B, the HTA concentration increased as the loading of BDDP increased, and the amount of OH produced increased.

＜試験例４：フロー式の固定床電解処理装置を用いたメチレンブルーの定電圧電解実験＞
試験例４では、図８に示す構成のフロー式の固定床電解処理装置２Ｂを使用して実験を行った。内容積５．５ｍＬの電解槽５０Ｂの内部には、製造例２で得たＢＤＤＰ（粒子径：４０μｍ～６０μｍ）を所定量（０．８ｇ、１．６ｇ、２．４ｇ）だけ充填して固定床電極（ＢＤＤＰ充填電極）４０Ｂの充填層４１Ｂを構成した。固定床電極４０Ｂの集電体４２Ｂとしては白金線を使用し、対電極２０Ｂとしては白金メッシュを使用した。なお、充填層４１Ｂの上流側（図中下側）にはフィルタ４３Ｂを配置したが、下流側（図中上側）にはフィルタを配置しなかった。<Test Example 4: Constant-voltage electrolysis experiment of methylene blue using a flow-type fixed-bed electrolysis apparatus>
In Test Example 4, an experiment was conducted using a flow-type fixed-bed electrolysis apparatus 2B configured as shown in FIG. A predetermined amount (0.8 g, 1.6 g, 2.4 g) of BDDP (particle diameter: 40 μm to 60 μm) obtained in Production Example 2 is filled and fixed inside the electrolytic cell 50B having an internal volume of 5.5 mL. A filling layer 41B of a floor electrode (BDDP filling electrode) 40B was constructed. A platinum wire was used as the current collector 42B of the fixed bed electrode 40B, and a platinum mesh was used as the counter electrode 20B. Note that the filter 43B was arranged on the upstream side (lower side in the drawing) of the filling layer 41B, but no filter was arranged on the downstream side (upper side in the drawing).

支持電解質として０．１Ｍ 硫酸ナトリウムを含有する５０μＭ メチレンブルー水溶液を調製し、このメチレンブルー水溶液３０ｍＬをプランジャーポンプにより循環させながら、５Ｖ、３６０分間の定電圧電解を行い、メチレンブルー濃度の減少量を定量した。 A 50 μM methylene blue aqueous solution containing 0.1 M sodium sulfate as a supporting electrolyte was prepared, and constant voltage electrolysis was performed at 5 V for 360 minutes while circulating 30 mL of this methylene blue aqueous solution with a plunger pump to quantify the decrease in methylene blue concentration. .

ＢＤＤＰ充填量を０．８ｇ、１．６ｇ、又は２．４ｇとし、流速を２．０ｍＬ／ｍｉｎとしたときのメチレンブルー濃度の時間変化を図９に示す。また、ＢＤＤＰ充填量を０．８ｇ又は１．６ｇとし、流速を０．５ｍＬ／ｍｉｎ又は２．０ｍＬ／ｍｉｎとしたときのメチレンブルー濃度の時間変化を図１０に示す。図９及び図１０は、メチレンブルーの初期濃度を１００％としたときの相対値を表したものである。図９及び図１０に示すとおり、ＢＤＤＰ充填量が増加するほどメチレンブルー濃度の減少量が増加した。また、流速を２．０ｍＬ／ｍｉｎとした場合よりも、流速は０．５ｍＬ／ｍｉｎとした場合の方がメチレンブルー濃度の減少量が大きかった。これは、ＢＤＤＰ充填電極の下流側にフィルタを配置しなかったため、流速を２．０ｍＬ／ｍｉｎとした場合には充填層が崩れたためと推測される。 FIG. 9 shows changes in methylene blue concentration over time when the BDDP filling amount is 0.8 g, 1.6 g, or 2.4 g and the flow rate is 2.0 mL/min. FIG. 10 shows changes in methylene blue concentration over time when the BDDP filling amount is 0.8 g or 1.6 g and the flow rate is 0.5 mL/min or 2.0 mL/min. 9 and 10 show relative values when the initial concentration of methylene blue is 100%. As shown in FIGS. 9 and 10, the amount of decrease in methylene blue concentration increased as the loading of BDDP increased. In addition, the decrease in methylene blue concentration was greater when the flow rate was 0.5 mL/min than when the flow rate was 2.0 mL/min. It is presumed that this is because no filter was arranged downstream of the BDDP filling electrode, so that the filling layer collapsed when the flow rate was set to 2.0 mL/min.

１，１Ａ 固定床電解処理装置（バッチ式）、２，２Ｂ 固定床電解処理装置（フロー式）、１０，１０Ａ 固定床電極、１１，１１Ａ 充填層、１２，１２Ａ 集電体、２０，２０Ａ，２０Ｂ 対電極、３０，３０Ａ 電解槽、４０，４０Ｂ 固定床電極、４１，４１Ｂ 充填層、４２，４２Ｂ 集電体、４３ａ，４３ｂ，４３Ｂ フィルタ、５０，５０Ｂ 電解槽 1, 1A fixed bed electrolysis device (batch type), 2, 2B fixed bed electrolysis device (flow type), 10, 10A fixed bed electrode, 11, 11A packed bed, 12, 12A current collector, 20, 20A, 20B counter electrode, 30, 30A electrolytic cell, 40, 40B fixed bed electrode, 41, 41B filling layer, 42, 42B current collector, 43a, 43b, 43B filter, 50, 50B electrolytic cell

Claims (5)

被処理水を電気化学的に処理する固定床電解処理装置であって、
導電性ダイヤモンド粒子の充填層を有する、陽極としての固定床電極と、
陰極としての対電極と、
前記固定床電極及び前記対電極が配置されるとともに、前記被処理水が通液される流路を有する電解槽と、
を備え、
前記導電性ダイヤモンド粒子が、ダイヤモンドからなる粒子状基材の表面に導電性ダイヤモンド層が形成されたものであり、
前記固定床電極が前記流路の上流側に配置され、且つ、前記対電極が前記流路の下流側に配置されるか、又は、前記固定床電極が前記流路の下流側に配置され、且つ、前記対電極が前記流路の上流側に配置され、
前記充填層が、前記流路の断面全体に亘って設けられる固定床電解処理装置。 A fixed-bed electrolytic treatment apparatus for electrochemically treating water to be treated,
a fixed bed electrode as an anode, having a packed bed of conductive diamond particles;
a counter electrode as a cathode ;
an electrolytic cell in which the fixed bed electrode and the counter electrode are arranged and which has a channel through which the water to be treated flows;
with
The conductive diamond particles are obtained by forming a conductive diamond layer on the surface of a particulate substrate made of diamond,
The fixed bed electrode is arranged upstream of the channel and the counter electrode is arranged downstream of the channel, or the fixed bed electrode is arranged downstream of the channel, and the counter electrode is arranged upstream of the channel,
A fixed-bed electrolysis apparatus in which the packed bed is provided over the entire cross section of the channel . 前記導電性ダイヤモンド層がボロンドープダイヤモンド層である請求項１に記載の固定床電解処理装置。 2. The fixed bed electrolytic treatment apparatus according to claim 1, wherein said conductive diamond layer is a boron-doped diamond layer . 前記固定床電極が、前記導電性ダイヤモンド粒子の充填層に電気的に接続した集電体を有する請求項１又は２に記載の固定床電解処理装置。 3. The fixed bed electrolytic treatment apparatus according to claim 1, wherein said fixed bed electrode has a current collector electrically connected to said packed bed of conductive diamond particles. 前記固定床電極が前記流路の上流側に配置され、且つ、前記対電極が前記流路の下流側に配置される請求項１～３のいずれか１項に記載の固定床電解処理装置。 The fixed bed electrolysis apparatus according to any one of claims 1 to 3 , wherein the fixed bed electrode is arranged on the upstream side of the channel, and the counter electrode is arranged on the downstream side of the channel. 請求項１～４のいずれか１項に記載の固定床電解処理装置の流路に被処理水を通液しながら電極間に電圧を印加することにより、前記被処理水を電気化学的に且つ連続的に処理する電解処理方法。 By applying a voltage between the electrodes while the water to be treated is passed through the flow path of the fixed bed electrolysis apparatus according to any one of claims 1 to 4 , the water to be treated is electrochemically and Continuous electrolysis method.
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