WO2021177270A1

WO2021177270A1 - Fixed-bed electrolysis treatment device and electrolysis treatment method

Info

Publication number: WO2021177270A1
Application number: PCT/JP2021/007832
Authority: WO
Inventors: 近藤　剛史; 駿介中村; 敏史東條; 湯浅　真
Original assignee: 学校法人東京理科大学
Priority date: 2020-03-02
Filing date: 2021-03-02
Publication date: 2021-09-10
Also published as: JPWO2021177270A1; JP7280650B2

Abstract

Provided is a fixed-bed electrolysis treatment device for electrochemically treating water to be treated, wherein the fixed-bed electrolysis treatment device is equipped with a fixed-bed electrode having a packed layer of conductive diamond particles; a counter electrode; and an electrolytic cell in which the fixed-bed electrode and the counter electrode are disposed and the water to be treated is passed through or housed. Also provided is an electrolysis treatment method that uses the fixed-bed electrolysis treatment device.

Description

Fixed-bed electrolysis equipment and electrolysis method

The present invention relates to a fixed bed electrolytic treatment apparatus and an electrolytic treatment method.

The conductive diamond electrode has a wider potential window than the platinum electrode and the like, can efficiently generate active species such as OH radical and ozone, and has excellent corrosion resistance. Therefore, for example, a factory. It is expected to be applied as an electrode for electrolysis when electrolyzing water to be treated such as wastewater.

Conductive diamond is generally formed on a substrate such as a silicon wafer by a chemical vapor deposition method (CVD method). Therefore, there is a problem that the shape of the electrode is limited to a thin film. Further, since the area of the obtained conductive diamond thin film depends on the size of the CVD apparatus, there is a problem that it is difficult to increase the surface area of the electrode.

In recent years, it has been proposed to apply conductive diamond particles to electrodes in order to solve these problems. According to such conductive diamond particles, the shape of the electrode is not limited to the thin film shape, and the surface area of the electrode can be easily increased.

For example, Patent Document 1 discloses a fluidized bed electrolysis treatment apparatus using conductive diamond particles as a fluidized bed electrode.

Japanese Unexamined Patent Publication No. 2008-36631

In the fluidized bed electrolysis treatment apparatus described in Patent Document 1, it is considered that the conductive diamond particles behave as bipolar electrodes, so that electrolysis occurs even when the particles are in a suspended state. Therefore, when the conductivity of the water to be treated is high, it is expected that the electrolysis efficiency will decrease.

An object of the present invention is to provide a fixed-bed electrolytic treatment apparatus capable of electrochemically treating even water to be treated having high conductivity, and an electrolytic treatment method using the fixed-bed electrolytic treatment apparatus.

Specific means for solving the above problems include the following embodiments.
<1> A fixed-bed electrolytic treatment device that electrochemically treats water to be treated.
A fixed floor electrode with a packed layer of conductive diamond particles,
With the counter electrode
An electrolytic cell in which the fixed floor electrode and the counter electrode are arranged, and in which the water to be treated is housed or passed,
A fixed-bed electrolysis treatment device provided with.
<2> The fixed bed electrolysis treatment apparatus according to <1>, wherein the conductive diamond particles are boron-doped diamond particles.
<3> The fixed bed electrolysis treatment apparatus according to <1> or <2>, wherein the fixed floor electrode has a current collector electrically connected to the packed layer of the conductive diamond particles.
<4> The fixed-bed electrolysis treatment apparatus according to any one of <1> to <3>, wherein the electrolytic cell has a flow path through which the water to be treated is passed.
<5> The fixed floor according to <4>, wherein one of the fixed floor electrode and the counter electrode is arranged on the upstream side or the downstream side of the flow path, and the other is arranged on the downstream side or the upstream side of the flow path. Electrolytic processing equipment.
<6> The fixed bed electrolysis treatment apparatus according to <5>, wherein the fixed floor electrode is arranged on the upstream side of the flow path and the counter electrode is arranged on the downstream side of the flow path.
<7> The fixed bed electrolysis treatment apparatus according to <5> or <6>, wherein the packed bed is provided in at least a part of a cross section of the flow path.
<8> The fixed bed electrolysis treatment apparatus according to <7>, wherein the packed bed is provided over the entire cross section of the flow path.
<9> An electrolytic treatment method for electrochemically treating water to be treated by applying a voltage between the electrodes of the fixed bed electrolytic treatment apparatus according to any one of <1> to <8>.
<10> The electrolytic treatment method according to <9>, which continuously treats the water to be treated.

According to the present invention, it is possible to provide a fixed-bed electrolytic treatment apparatus capable of electrochemically treating even water to be treated having high conductivity, and an electrolytic treatment method using the fixed-bed electrolytic treatment apparatus.

It is a figure which shows an example of the fixed bed electrolysis processing apparatus which concerns on this embodiment. It is a figure which shows another example of the fixed bed electrolysis processing apparatus which concerns on this embodiment. It is a figure which shows the cyclic voltammogram obtained in Test Example 1. It is a figure which shows the decrease amount of the methylene blue concentration after 60 minutes when the constant voltage electrolysis was performed at 3V, 4V, or 5V using the 50 μM methylene blue aqueous solution as the water to be treated in Test Example 2. In Test Example 2, it is a figure which shows the time change of the methylene blue concentration at the time of performing constant voltage electrolysis at 5V using a 50 μM methylene blue aqueous solution as water to be treated. It is a figure which shows the schematic structure of the batch type fixed bed electrolysis processing apparatus used in Test Example 3. It is a figure which 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 treatment apparatus of FIG. 6, and performing constant voltage electrolysis at 5 V for 30 minutes. 2-Hydroxyterephthalic acid (HTA) in the solution after 5 mL of 1 mM disophthalate terephthalate (NaTA) solution was added to the electrolytic cell of the fixed bed electrolysis treatment apparatus shown in FIG. 6 and constant voltage electrolysis was performed at 5 V for 30 minutes. It is a figure which shows the concentration. It is a figure which shows the schematic structure of the flow type fixed bed electrolysis treatment apparatus used in Test Example 4. In Test Example 4, it is a figure which shows the time change of the methylene blue concentration when the constant voltage electrolysis was performed at 5V at a flow rate of 2.0 mL / min using a 50 μM methylene blue aqueous solution as water to be treated. In Test Example 4, it is a figure which shows the time change of the methylene blue concentration when the constant voltage electrolysis was performed at 5V at a flow rate of 0.5 mL / min or 2.0 mL / min using a 50 μM methylene blue aqueous solution as water to be treated. ..

Hereinafter, specific embodiments to which the present invention is applied will be described in detail with reference to the drawings.

The fixed bed electrolysis treatment device according to the present embodiment is a fixed bed electrolysis treatment device that electrochemically treats water to be treated, and is fixed with a fixed floor electrode having a packed layer of conductive diamond particles, a counter electrode, and the like. A floor electrode and a counter electrode are arranged, and an electrolytic cell in which water to be treated is housed or passed is provided. By applying a voltage between the electrodes of this fixed-bed electrolytic treatment apparatus, the water to be treated can be treated electrochemically.

In the following, the conductive diamond particles will be described first, and then the configuration of the fixed bed electrolysis treatment device will be described.

(Conductive diamond particles)
Examples of the 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. Examples of Group 13 or Group 15 elements include boron, nitrogen, phosphorus and the like.

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, and may have an aspect ratio of more than 1.

The particle size of the conductive diamond particles is, for example, preferably 1 μm to 1000 μm, and more preferably 20 μm to 100 μm.

Among the conductive diamond particles, boron-doped diamond particles (BDDP) doped with boron are preferable.

The method for producing BDDP is not particularly limited, and known production methods described in JP-A-2008-36631, JP-A-2018-76216, and the like can be adopted. A preferred production method includes a method of forming a boron-doped diamond layer (BDD layer) on the surface of the particulate substrate. Hereinafter, this manufacturing method will be described.

The particulate substrate is not particularly limited as long as it does not melt or deform when the BDD layer is formed, and can be appropriately selected depending on the intended purpose. Specific examples of the particulate substrate include natural or artificial diamond particles; silicon particles; metal particles such as molybdenum particles; metal oxide particles such as alumina particles; boron nitride particles, quartz particles; and the like. One type of these particulate base materials may be used alone, or two or more types may be used in combination. Of these, natural or artificial diamond particles are preferred.

The method of forming the BDD layer is not particularly limited and can be appropriately selected according to the purpose. Specific examples of the forming method include a CVD method such as a thermal CVD method, a plasma CVD method, and a thermal filament CVD method; a physical vapor deposition method (PVD method) such as an ion beam method and an ionization vapor deposition method; and a high temperature and high pressure method. .. Among these, the plasma CVD method is preferable.

In the above-mentioned CVD method, the carbon source and the boron source which are the raw materials of the BDD layer are not particularly limited. As the carbon source, methane, acetone or the like can be used. Further, as the boron source, diborane, trimethylborane, trimethoxyborane and the like can be used.

In the BDD layer, the amount of boron doped into diamond is preferably 10 ppm or more, more preferably 1000 ppm or more, and further preferably 10000 ppm or more with respect to the carbon constituting the diamond. The amount of boron doped in diamond can be measured by secondary ion mass spectrometry or the like.

(Example of fixed floor electrolysis treatment equipment)
An example of the fixed bed electrolysis treatment apparatus is shown in FIG. In the fixed bed electrolysis treatment device 1 shown in FIG. 1, a fixed floor electrode (anode) 10, a counter electrode (cathode) 20, a fixed floor electrode 10 and a counter electrode 20 are arranged, and water to be treated is housed. An electrolytic cell 30 is provided. The fixed bed electrolysis treatment device 1 shown in FIG. 1 is an example of a batch type fixed bed electrolysis treatment device that electrolyzes the water to be treated contained in the electrolytic cell 30.

The fixed floor electrode 10 has a packed layer 11 filled with the above-mentioned conductive diamond particles and a current collector 12 electrically connected to the packed 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.

The counter electrode 20 constitutes an electrode for electrolysis together with the fixed floor electrode 10. Examples of the counter electrode 20 include a platinum electrode, a gold electrode, a stainless steel electrode, a conductive diamond electrode and the like. The counter electrode 20 may be a fixed floor electrode having a packed layer of conductive diamond particles.

In the electrolytic cell 30, the above-mentioned fixed floor electrode 10 and counter electrode 20 are arranged, and water to be treated is housed. The electrolytic cell 30 may be provided with a stirrer for stirring the water to be treated.

According to the fixed bed electrolysis treatment device 1 described above, the water to be treated contained in the electrolytic cell 30 can be electrolyzed by applying a voltage between the fixed floor electrode 10 and the counter electrode 20. It is known that an electrode using conductive diamond has a wide potential window, suppresses electrolysis of water, and facilitates an electrolytic reaction of organic substances and the like. Therefore, for example, when the water to be treated contains an organic substance, the organic substance can be efficiently decomposed by active species such as OH radicals and ozone generated by applying a voltage. Moreover, in the present embodiment, since the conductive diamond particles are arranged as the fixed floor electrodes, the surface area of the electrodes can be expanded and the electrolysis efficiency can be improved. When the water to be treated contains metal ions, the metal ions can be reduced by applying a voltage to recover the metal.

The voltage and its application time when electrolyzing the water to be treated are not particularly limited, and can be appropriately selected according to the type of water to be treated and the like.

(Other examples of fixed floor electrolysis treatment equipment)
Another example of the fixed bed electrolysis treatment apparatus is shown in FIG. The fixed bed electrolysis treatment device 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 which has passed through the electrolytic cell. It is different from the fixed bed electrolytic cell 1 shown in. Therefore, the same reference numerals are given to the configurations common to those in FIG. 1, and detailed description thereof will be omitted.

In the fixed bed electrolysis treatment device 2 shown in FIG. 2, a fixed floor electrode (anode) 40, a counter electrode (cathode) 20, a fixed floor electrode 40 and a counter electrode 20 are arranged, and water to be treated is passed through the fixed bed electrolysis treatment device 2. An electrolytic cell 50 having a flow path is provided. The fixed-bed electrolysis treatment device 2 shown in FIG. 2 is an example of a flow-type fixed-bed electrolysis treatment device that continuously electrolyzes the water to be treated that has passed through the electrolytic cell 50.

The fixed floor electrode 40 is filled with the above-mentioned conductive diamond particles, and is inserted into the filling layer 41 and the filling layer 41 provided over the entire cross section of the flow path through which the water to be treated is passed. It has a current collector 42 and a pair of

filters

43a and 43b provided so as to sandwich the packed bed 41. Examples of the material of 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 they allow water to be treated to pass through and the pore size is smaller than the particle size of the conductive diamond particles.

The electrolytic cell 50 has a flow path through which the water to be treated is passed in the direction of the arrow in the figure (direction from the lower side to the upper side in the figure), the fixed floor electrode 40 is arranged on the upstream side, and the fixed floor electrode 40 is arranged. The counter electrode 20 is arranged on the downstream side.

According to the fixed bed electrolysis treatment device 2 described above, by applying a voltage between the fixed floor electrode 40 and the counter electrode 20, the water to be treated that has passed through the electrolytic cell 50 is continuously electrolyzed. be able to.

In particular, in the fixed bed electrolysis treatment device 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 passes, the water to be treated reliably forms the filling layer 41. It will pass through, and more efficient electrolytic treatment will be possible. For example, when the water to be treated contains an organic substance, the organic substance can be decomposed more efficiently by an active species such as OH radical generated by applying a voltage.

In the fixed bed electrolytic treatment apparatus 2 shown in FIG. 2, the fixed floor electrode 40 is arranged on the upstream side of the flow path and the counter electrode 20 is arranged on the downstream side of the flow path, but the present invention is limited to this example. Instead, the fixed floor electrode 40 may be arranged on the downstream side of the flow path, and the counter electrode 20 may be arranged on the upstream side of the flow path.

Further, in the fixed bed electrolytic treatment apparatus 2 shown in FIG. 2, the filling layer 41 is provided over the entire cross section of the flow path, but the present invention is not limited to this example, and at least a part of the cross section of the flow path is provided. It suffices if it is provided in.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

<Manufacturing Example 1: Manufacture of Boron Doped Diamond Thin Film (BDD Thin Film)>
The surface of the silicon wafer was scratched with diamond particles having a particle size of 3 μm to 6 μm, and then ultrasonically cleaned with methanol, acetone, and ultrapure water for 30 minutes each. Next, a BDD thin film was formed on the silicon wafer by the microwave plasma CVD method. The film forming conditions were microwave output: 5500 W, stage temperature: 698 ° C., chamber internal pressure: 90 Torr, plenum pressure: 70 Torr, film forming time: 4 hours, and boron concentration: 10000 ppm.

<Manufacturing Example 2: Production of Boron Doped Diamond Particles (BDDP)>
As the particulate substrate, diamond particles having a particle size of 40 μm to 60 μm were used. First, in order to remove impurities (Co, Fe, various sp ² carbons, etc.) contained in the diamond particles, cleaning was performed according to the previously reported. Specifically, diamond particles are immersed in royal water in which hydrochloric acid and nitric acid are mixed at a volume ratio of 3: 1 and heated at 60 ° C. for 30 minutes, and then immersed in 30% hydrogen peroxide solution at 60 ° C. It was heated for 30 minutes. Then, it was washed sequentially with ultrapure water, 2-propanol, and acetone, 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 a microwave plasma CVD method to obtain BDDP. The film forming conditions were microwave output: 1300 W, stage temperature: 800 ° C., chamber internal pressure: 50 Torr, film forming time: 8 hours, and boron concentration: 20000 ppm.

<Manufacturing Example 3: Manufacture of Fixed Floor Electrolysis Treatment Equipment>
On the BDD thin film (2 cm × 2 cm) obtained in Production Example 1, ^{a tubular part obtained by cutting a centrifugal tube (inner area: 1 cm 2} ) to a length of 10 cm was fixed. ^{At that time, an O-ring (inner area: 1 cm 2} ) was interposed between the tubular part and the BDD thin film so that liquid leakage did not occur. Next, the inside of the tubular part was filled with the BDDP (particle size: 40 μm to 60 μm) obtained in Production Example 2 in a predetermined amount to form a fixed floor electrode (hereinafter, referred to as “BDDP-filled electrode”). Then, a batch-type fixed-bed electrolysis treatment apparatus having the configuration shown in FIG. 1 was manufactured using a platinum wire as a counter electrode. In Test Examples 1 and 2 shown below, an experiment was conducted using this batch type fixed bed electrolysis treatment device.

<Test Example 1: Evaluation of electrode surface area of BDDP-filled electrode>
Background current 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 the electrode surface area of the BDDP-filled electrode is increased by increasing the filling amount of BDDP. The size of was compared. The CV measurement was carried out in a 0.1 M aqueous sodium sulfate 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.

The cyclic voltammogram obtained by CV measurement is shown in FIG. As shown in FIG. 3, the background current when the BDDP filling electrode was used was larger than the background current when the BDD thin film electrode was used, and the value increased as the filling amount of BDDP increased. 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 the electrode surface area of the BDDP-filled electrode is increased by increasing the filling amount of BDDP.

<Test Example 2: Constant-voltage electrolysis experiment of methylene blue using a batch-type fixed-bed electrolysis treatment device>
An aqueous solution containing methylene blue was used as water to be treated, and a constant voltage electrolysis experiment was carried out using a BDDP-filled electrode or a BDD thin film electrode. By using methylene blue, it is possible to quantify by the ultraviolet-visible (UV-vis) absorption spectrum.

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) was prepared. : 0 g) was added to the electrolytic cell of the electrolytic treatment apparatus provided with 5 mL. Then, constant voltage electrolysis was performed for 60 minutes to quantify the amount of decrease in methylene blue concentration. The constant voltage was 3V, 4V, or 5V. When quantifying the amount of decrease in the methylene blue concentration, the supernatant of the methylene blue aqueous solution was collected and UV-vis measurement was performed. Then, the obtained absorbance was converted into a methylene blue concentration by a calibration curve prepared in advance.

FIG. 4 shows the amount of decrease in the methylene blue concentration when constant voltage electrolysis was performed for 60 minutes. As shown in FIG. 4, as the applied voltage increased and the BDDP filling amount increased, the amount of decrease in the methylene blue concentration increased.

In addition, in order to investigate the time change of the methylene blue concentration when constant voltage electrolysis was performed, 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 above. The supernatant liquid used for the measurement was returned to the electrolytic cell without being made into a waste liquid.

FIG. 5 shows the time change of the methylene blue concentration when constant voltage electrolysis of 5 V was performed. FIG. 5 shows a relative value 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 significantly at the initial stage of the electrolytic treatment, and the decrease rate decreased as the methylene blue concentration decreased.

<Test Example 3: Evaluation of OH radical generation by batch type fixed bed electrolysis treatment device>
In Test Example 3, an experiment was conducted using a batch-type fixed-bed electrolytic treatment apparatus 1A having the configuration shown in FIG. Inside the electrolytic cell 10A having an internal volume of 5.5 mL, 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 is placed. ) To form a packed layer 11A of a fixed floor electrode (BDDP filled electrode) 10A. A platinum wire was used as the current collector 12A and the counter electrode 20A of the fixed floor electrode 10A.

Add 5 mL of 1.0 mM disodium terephthalate (NaTA) solution to the electrolytic cell, perform constant voltage electrolysis at 5 V for 30 minutes, and then measure the fluorescence intensity at a wavelength of 425 nm to obtain 2-hydroxyterephthalate in the solution. The concentration of acid (HTA) was measured. Since NaTA is converted to HTA by the OH radicals generated by the electrolytic treatment, the amount of OH radicals produced can be indirectly evaluated by measuring the concentration of HTA.

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, it can be seen that the HTA concentration increased as the BDDP filling amount increased, and the OH production amount increased.

<Test Example 4: Constant-voltage electrolysis experiment of methylene blue using a flow-type fixed-bed electrolysis treatment device>
In Test Example 4, an experiment was conducted using a flow-type fixed-bed electrolytic treatment apparatus 2B having the configuration shown in FIG. The inside of the electrolytic cell 50B having an internal volume of 5.5 mL is filled with the BDDP (particle size: 40 μm to 60 μm) obtained in Production Example 2 by a predetermined amount (0.8 g, 1.6 g, 2.4 g) and fixed. The packed layer 41B of the floor electrode (BDDP filled electrode) 40B was constructed. A platinum wire was used as the current collector 42B of the fixed floor electrode 40B, and a platinum mesh was used as the counter electrode 20B. The filter 43B was arranged on the upstream side (lower side in the figure) of the packed bed 41B, but the filter was not arranged on the downstream side (upper side in the figure).

A 50 μM methylene blue aqueous solution containing 0.1 M sodium sulfate was prepared as a supporting electrolyte, and 30 mL of this methylene blue aqueous solution was circulated by a plunger pump and subjected to constant voltage electrolysis at 5 V for 360 minutes to quantify the decrease in methylene blue concentration. ..

FIG. 9 shows the time change of the methylene blue concentration when the BDDP filling amount was 0.8 g, 1.6 g, or 2.4 g and the flow rate was 2.0 mL / min. Further, FIG. 10 shows the time change of the methylene blue concentration 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 the methylene blue concentration increased as the BDDP filling amount increased. In addition, the amount of decrease in the methylene blue concentration was larger when the flow velocity was 0.5 mL / min than when the flow velocity was 2.0 mL / min. It is presumed that this is because the filter was not arranged on the downstream side of the BDDP filling electrode, and the filling layer collapsed when the flow velocity was 2.0 mL / min.

1,1A fixed bed electrolyzer (batch type), 2,2B fixed bed electrolyzer (flow type), 10,10A fixed floor electrode, 11,11A packing layer, 12,12A current collector, 20,20A, 20B counter electrode, 30, 30A electrolytic cell, 40, 40B fixed floor electrode, 41, 41B packing layer, 42, 42B current collector, 43a, 43b, 43B filter, 50, 50B electrolytic cell

Claims

A fixed-bed electrolytic treatment device that electrochemically treats water to be treated.
A fixed floor electrode with a packed layer of conductive diamond particles,
With the counter electrode
An electrolytic cell in which the fixed floor electrode and the counter electrode are arranged, and in which the water to be treated is housed or passed,
A fixed-bed electrolysis treatment device provided with.
The fixed bed electrolysis treatment apparatus according to claim 1, wherein the conductive diamond particles are boron-doped diamond particles.
The fixed bed electrolysis treatment apparatus according to claim 1 or 2, wherein the fixed floor electrode has a current collector electrically connected to the packed layer of the conductive diamond particles.
The fixed-bed electrolysis treatment apparatus according to any one of claims 1 to 3, wherein the electrolytic cell has a flow path through which the water to be treated is passed.
The fixed bed electrolysis treatment apparatus according to claim 4, wherein one of the fixed floor electrode and the counter electrode is arranged on the upstream side or the downstream side of the flow path, and the other is arranged on the downstream side or the upstream side of the flow path. ..
The fixed bed electrolysis treatment apparatus according to claim 5, wherein the fixed floor electrode is arranged on the upstream side of the flow path, and the counter electrode is arranged on the downstream side of the flow path.
The fixed bed electrolysis treatment apparatus according to claim 5 or 6, wherein the packed bed is provided in at least a part of a cross section of the flow path.
The fixed bed electrolysis treatment apparatus according to claim 7, wherein the packed bed is provided over the entire cross section of the flow path.
An electrolytic treatment method for electrochemically treating water to be treated by applying a voltage between the electrodes of the fixed bed electrolytic treatment apparatus according to any one of claims 1 to 8.
The electrolytic treatment method according to claim 9, wherein the water to be treated is continuously treated.