JPH0416286A - Electrochemical treatment of water to be treated - Google Patents

Abstract

PURPOSE:To conserve water and fuel cost by supplying water to be treated containing oily dispersed matter (phenol extract) to a fixed bed type three- dimensional electrode-electrolytic cell to electrochemically treat the same. CONSTITUTION:When a current is supplied to a fixed bed type three-dimensional electrode-electrolytic cell 2, for example, while bath water is supplied to said electrolytic cell 2 from below, as shown by an arrow, the under and upper surfaces of each of fixed beds 5 are respectively polarized positively and negatively to generate potential in the fixed beds 5 and across the fixed beds 5, and the bath water flowing through the electrolytic cell 2 comes into contact with the positively polarized places of the fixed beds 5 having said potential to decompose the phenol extract dispersed in the bath water and is taken out of the electrolytic cell 2 from the upper part thereof. By this method, the bath water can be purified and, if necessary, insoluble matter is filtered by a filter to almost perfectly soluble and insoluble impurities and the used bath water is used over a long period of time without being discharged to make is possible to conserve the amount of used water and fuel.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for electrochemically treating water to be treated in order to suppress various performance deteriorations of water to be treated containing an oily dispersion. More specifically, by electrochemically treating water containing oil and fatty acids discharged from the human body using a three-dimensional electrode electrolytic cell, the oil and fatty acids in the water are decomposed. Concerning methods for doing so.

(Prior art) The amount of bath water used has increased due to the spread of household bathtubs and the hot spring boom in recent years, but as the bath water continues to be used, oils such as human body grime and fatty acid components float in the bath water. It cannot be used for a long time. However, if this oil content could be easily decomposed or removed, it would be possible to use bath water for a long period of time and save on fuel costs.

(Problems to be Solved by the Invention) As mentioned above, there is a desire for a method that can effectively decompose or remove oil components dispersed in conventional bath water and the like.

(Object of the Invention) An object of the present invention is to eliminate the drawbacks of the prior art described above and provide a method for treating water to be treated having dispersed oil to decompose or remove the oil.

(Means for Solving the Problems) The present invention is characterized in that water to be treated containing an oily dispersion is supplied to a fixed bed type three-dimensional electrode electrolytic cell, and the water to be treated is electrochemically treated. This is a method for treating water to be treated.

In addition, in the present invention, since an electrochemical reaction such as a substantial redox reaction may not occur on the electrode surface, the tank used in the method of the present invention should be called an electrochemical processing device, but it is not commonly used. According to the name, it is called an electrolytic cell.

The present invention will be explained in detail below.

The present invention supplies water to be treated, such as bath water or hot spring water, containing an oily dispersed substance to a fixed bed type three-dimensional electrode electrolytic cell, applies a DC or AC voltage to the electrolytic cell, and processes the oily dispersed substance contained in the bath water or the like by applying a DC or AC voltage to the electrolytic cell. It is characterized by decomposing or removing.

The oily dispersion removed by the method of the present invention means a phenol extract, and contains oil and fatty acid components.

The water to be treated, such as bath water used in domestic bathtubs and public baths, must be kept clean at all times because it comes into contact with the human body. and fatty acids, i.e., phenolic extractables. In commercial bathhouses such as public baths and hot springs that use large amounts of bath water, the bath water is circulated and the phenol extracted substances are removed using filters, etc.
Usually, sufficient removal efficiency cannot be obtained.

When cough water to be treated is supplied to a fixed bed type three-dimensional electrode electrolyzer,
The phenol extracted substance in the water to be treated comes into contact with the anode and cathode of the electrolytic cell, or the dielectric material and particles for forming a fixed bed, which will be described later, due to liquid flow, and undergoes a strong oxidation reaction, especially on the surface of the anode, and the surface of the cathode. It is thought that the phenol extracted substances are removed by undergoing a strong reduction reaction at which at least a portion of them is decomposed into carbon dioxide and water.

Therefore, in the method of the present invention, it is not enough for the phenol extracted substances in the water to be treated to come into contact with electrodes to which a voltage is applied, dielectric materials, particles for forming defined beds, etc., and the phenol extracted substances dispersed in the water to be treated are Sufficient voltage must be applied between the poles to decompose the material.

Therefore, in the present invention, the potential of the anode where the decomposition of the phenol extract material occurs is set to +0.2 to -1.2 V (vs.
It is desirable to degrade the phenolic extractables as fully as possible (SHE).

However, in the case of water to be treated that requires large-scale treatment, such as bath water, the amount of electricity required to decompose the phenol extract by the method of the present invention often accounts for a large portion of the treatment cost.

The amount of electricity is expressed as [power] = [voltage] x [current]. If no current flows and no gas is generated, the amount of electricity is zero, but if a current flows that generates gas, it is processed. Since the amount of water required is important, the amount of power consumed is also important. The minimum voltage value required for decomposition of phenol extractables is approximately constant, and therefore the current value must be reduced in order to minimize power consumption. If the amount of water to be treated is small and the current flowing is also small, an increase or decrease in the current value will not have much of an effect on the power consumption. The reduction is large and reduces power consumption. The electrolysis voltage in a normal electrolytic cell is [voltage drop due to resistance between the anode terminal and the anode] +
[Theoretical electrolysis voltage of the anode] + [Overvoltage of the anode] + [Voltage drop due to solution resistance] ↓ [Theoretical electrolysis voltage of the cathode] + [Overvoltage of the cathode] + [Voltage drop due to the resistance between the cathode terminal and the cathode] be done.

According to Ohm's law, there is a relationship of [voltage] = [current] x [resistance], and as mentioned above, the minimum voltage value is almost determined, so in order to reduce the current value, it is necessary to increase the resistance. . There are various factors that affect the resistance, but the factor that has the greatest effect is the resistance of the electrolytic solution, that is, the water to be treated in the present invention.

The resistance of the water to be treated is determined by the resistivity of the water itself and the distance between the poles, and it is not practical to increase or decrease the resistivity of the water to be treated, so in reality, the resistance value is adjusted by adjusting the distance between the poles. can be set to a predetermined value. In other words, when treating bath water, etc., according to the present invention, by increasing the distance between the poles, the resistance of the water to be treated is increased and the current value is decreased, thereby reducing power consumption, thereby achieving economical operation. It is desirable to make it possible. Therefore, in the three-dimensional electrode type electrolytic cell used in the present invention, it is preferable to provide a sufficient distance between the three-dimensional electrode, which is normally used as an anode, and the cathode, which is a counter electrode.

When gas is generated when processing a large amount of water such as bath water, the gases that are generated, that is, oxygen gas and hydrogen gas, are usually generated at a mixing ratio within the explosive limit, and in order to avoid the risk of explosion, inert gas such as air is used. It is desirable to dilute the electrolytic gas with gas, for example, by installing a means for separating the electrolytic gas generated at the outlet of the electrolytic cell and a means for diluting the electrolytic gas after separation with air so that the electrolytic gas concentration becomes 4% by volume or less. be able to.

It is preferable that the electrolytic cell used for treating water to be treated, such as bath water, which requires large-scale treatment, be a bipolar fixed-bed three-dimensional electrode electrolytic cell. In the case of these types of water to be treated, the amount of water to be treated is, for example, several tons per hour,
It is desirable to use a bipolar fixed bed electrolytic cell, which is an electrolytic cell with a high processing capacity per unit volume of the electrolytic cell, and by using this electrolytic cell, the contact area with the water to be treated can be increased, This is advantageous in that the device size can be reduced and the efficiency of electrolysis can be increased.

Furthermore, tap water contains calcium and magnesium ions other than the aforementioned microorganisms, and clogging of pipes due to precipitation of these ions as hydroxides on the inner walls of tap water pipes has become a major problem. In many cases, bath water that uses tap water as a water source also contains calcium ions and magnesium ions, and these ions adhere to pipes.

When the treated water is electrochemically treated using a fixed-bed three-dimensional electrode electrolytic cell, the calcium ions and magnesium ions in the water to be treated are hydroxylated on the cathode or three-dimensional electrode of the electrolytic cell. As a substance, it is deposited on the cathode and removed.

The electrolytic cells used in the method of the present invention are fixed-bed three-dimensional electrode electrolytic cells, that is, fixed-bed monopolar electrolytic cells and fixed-bed bipolar electrolytic cells. Since the electrode has a large surface area, it is possible to increase the contact area between the electrode surface and the water to be treated such as bath water.

The electrodes in the fixed bed type three-dimensional electrode electrolytic cell of the present invention generally include a three-dimensional electrode and a power supply electrode, and the three-dimensional electrode has a shape corresponding to the electrolytic cell used as described above, and is a fixed bed type bipolar type. When using an electrolytic cell, a porous material through which the water to be treated can pass, such as granular, spherical, felt, woven fabric,
Carbon-based materials such as activated carbon, graphite, carbon fiber, etc. that have a porous block shape, or metal materials such as nickel, copper, stainless steel, iron, titanium, etc. that have the same shape, and coatings of precious metals on these metal materials. a plurality of preferably granular, spherical,
A dielectric material in the form of a fiber, felt, woven cloth, porous block, or sponge is placed in a DC electric field, and from a porous plate such as a flat plate, expanded mesh, or perforated plate installed at both ends. A fixed-bed type bipolar housing containing a three-dimensional electrode formed by applying a DC voltage or an AC voltage between the power feeding electrodes to polarize the dielectric and forming an anode and a cathode at one end and the other end of the dielectric, respectively. In addition, it is possible to create a fixed-bed bipolar electrolyzer by installing three-dimensional materials that function individually as an anode or as a cathode alternately so that they do not short-circuit and electrically connect them. It can be a tank.

When using a carbon-based material such as activated carbon, graphite, or carbon fiber as the dielectric and treating water while generating oxygen gas from the anode, the dielectric is oxidized by the oxygen gas and dissolved as carbon dioxide gas. It becomes easier to do. In order to prevent this, a porous material that is usually used as an insoluble metal electrode is coated with a platinum group metal oxide such as iridium oxide or ruthenium oxide on a base material such as titanium on the anodic polarization side of the dielectric. They may be placed in contact so that oxygen evolution occurs primarily on the porous material.

In addition, as another type of fixed-bed bipolar electrolytic cell, for example, a power feeding anode and a cathode are installed in a cylindrical electrolytic cell body, and a large number of conductive electrodes that function as three-dimensional electrodes are installed between the two power feeding electrodes. There is an electrolytic cell in which particles for forming a fixed bed and insulating particles made of electrically insulating synthetic resin or the like are mixed almost uniformly in a smaller number than the particles for forming a fixed bed. In the electrolytic cell, when electricity is applied between both power feeding electrodes to apply a potential, the fixed bed forming particles are polarized in the same way as the dielectric, one end of which is positively charged and the other end of which is negatively charged, forming each fixed bed. An electric potential is generated in the particles, giving each particle the ability to decompose phenol extractable substances in the water to be treated. The insulating particles have a function of preventing the repowering electrode from being electrically connected to the conductive fixed bed forming particles and causing a short circuit.

In addition, when using a monopolar fixed bed electrolytic cell, one of the above-mentioned dielectrics or three-dimensional materials that function alone as an anode or a cathode may be placed in the electrolytic cell with or without a diaphragm. Make sure to install it.

Regardless of which type of electrode is used, if there is a gap in the electrolytic cell through which the water to be treated flows, allowing the liquid to flow without coming into contact with the electrodes, dielectrics, or particulates, the treatment efficiency of the water to be treated will decrease. Therefore, it is desirable to arrange the electrodes and the like so that the flow of the water to be treated in the electrolytic cell does not become short-circuited.

The flow rate of the water to be treated that is supplied to the electrolytic cell may be determined so that the water to be treated can efficiently contact the surfaces of the electrodes, etc. If the flow is completely laminar, there will be little lateral movement and ,
Since contact with the dielectric material and the particle surface is reduced, it is preferable to form a turbulent flow state, and it is particularly preferable to form a turbulent flow having a Reynolds number of 500 or more.

Even if the inside of the electrolytic cell is divided by a diaphragm to form an anode chamber and a cathode chamber, electricity can be applied as is without using a diaphragm, but a diaphragm is not used to ensure smooth flow of the water to be treated. This is desirable. In this case, if the distance between the electrodes, the dielectric and the electrode, or the distance between the dielectrics is to be narrowed, an electrically insulating spacer such as a mesh spacer made of an organic polymer material is used between the two electrodes to prevent short circuits. Alternatively, it is preferable to insert it between the dielectric materials or the like. In addition, when using a diaphragm, it is desirable to use a porous membrane, for example, one with an aperture ratio of 10% to 95%, preferably 20% to 80%, so as not to obstruct the movement of flowing water to be treated. The diaphragm must have micropores with a pore diameter that is at least large enough to allow the water to be treated to pass therethrough.

For example, when an electrolytic cell with such a configuration is used to decompose phenol extracts from bath water, it can be connected to a domestic bathtub, a bathtub in a commercial bathhouse such as a public bathhouse or a hot spring, or to the supply piping for these bathtubs. By introducing at least part, preferably all, of the bath water into the electrolytic cell and electrochemically treating it, it is possible to decompose the phenol-extracted substances in the bath water, thereby purifying the bath water. By filtering insoluble substances with a filter as necessary, soluble and insoluble impurities are almost completely removed, and used bath water can be used for a long time without being disposed of, reducing the amount of water used and the amount of fuel used. savings can be achieved.

In addition, in the electrolytic cell used in the method of the present invention, a leakage current may occur in the electrolytic cell, and the leakage current may flow from the electrolytic cell through the water to be treated into other parts, causing elution of the parts. The back part of the electrode where the anode and cathode do not face each other and/or
Alternatively, the leakage current can be interrupted by installing a member having higher conductivity than the liquid to be treated in the inlet/outlet pipe of the electrolytic cell so that one end thereof can be grounded.

Next, a preferred example of an electrolytic cell that can be used in the present invention will be described based on the accompanying drawings, but the electrolytic cell that can be used in the method of the present invention is not limited to this electrolytic cell.

FIG. 1 is a schematic longitudinal cross-sectional view showing an example of a fixed bed bipolar electrolytic cell that can be used as an electrolytic cell in the method of the present invention.

A mesoche-shaped power feeding anode terminal 3 and a power feeding cathode terminal 4 are provided near the upper and lower ends of the cylindrical electrolytic cell body 2 having flanges 1 on the upper and lower sides, respectively. The electrolytic cell body 2 is preferably formed of an electrically insulating material that can withstand long-term use or repeated use.
In particular, synthetic resins such as polyepichlorohydrin, polyvinyl methacrylate, polyethylene, polypropylene, polyvinyl chloride, polyethylene chloride, and phenol-formaldehyde resins can be preferably used.

The anode terminal 3 that provides a positive DC voltage is made of, for example, a carbon material (e.g. activated carbon, charcoal, coke, coal, etc.), a graphite material (e.g. carbon fiber, carbon cloth, graphite, etc.), a carbon composite material (e.g. carbon with metal added to it). activated carbon fiber non-woven fabric (e.g. K
E-1000 felt, Toyobo Co., Ltd.), or a material made of platinum, platinum, palladium or nickel supported on it,
Further, the electrode is made of a dimensionally stable electrode (platinum group oxide coated titanium material), platinum coated titanium material, nickel material, stainless steel material, iron material, etc. The cathode terminal 4, which faces the anode terminal 3 and applies a negative DC voltage, is made of, for example, platinum, stainless steel, titanium, nickel, copper, Hastelloy, graphite, carbon material, mild steel, or a metal material coated with a platinum group metal. ing.

A plurality of sponge-like fixed beds 5, in the illustrated example, are stacked between the two electrode terminals 3.4, and between the fixed beds 5 and between the fixed bed 5 and the two electrode terminals 3.4. Four porous diaphragms or spacers 6 are sandwiched between them. Each fixed bed 5 is in close contact with the inner wall of the electrolytic cell main body 2, and does not pass through the inside of the fixed bed 5, so that the leakage flow of the water to be treated flowing between the fixed bed 5 and the side wall of the electrolytic cell main body 2 is minimized. It is located in When a diaphragm is used, the diaphragm may be a woven cloth, an unglazed plate, a particle sintered plastic, a perforated plate,
An ion exchange membrane or the like is used, and a woven cloth, perforated plate, net, rod-shaped material, etc. made of an electrically insulating material is used as a spacer.

When an electric current is supplied to the electrolytic cell having such a configuration while supplying bath water, for example, from below as shown by the arrow, each of the fixed beds 5 is polarized with the lower surface being positively polarized and the upper surface being negatively polarized as shown in the figure. 5 and between the fixed bed 5 and the bath water flowing through the electrolytic cell contacts the positively polarized part of the fixed bed 5 which has this potential, and the phenol extracted substances dispersed in the water to be treated are decomposed. After that, it is taken out above the electrolytic cell.

FIG. 2 shows another example of a bipolar fixed bed electrolytic cell that can be used in the present invention. A mesh-like insoluble metal material 7 is installed in close contact with the side to be positively polarized, and since the other members are the same as those in FIG. 1, they are given the same reference numerals and their explanation will be omitted.

The fixed bed 5 to which a DC voltage is applied is most polarized at both ends thereof, and when gas is generated, the most intense gas generation occurs at both ends. Therefore, dissolution occurs fastest at the end of the fixed bed 5 facing the power supply cathode 4 where the polarization is strongest, that is, where oxygen gas is most intensely generated. As shown in the figure, if the insoluble metal material 7 is installed in this part, most of the oxygen gas will be removed from the insoluble metal material 7 because the overvoltage of the insoluble metal material 7 is lower than the overvoltage of the carbon-based material forming the fixed bed 5. Since the fixed bed 5 hardly comes into contact with oxygen gas, the dissolution of the fixed bed 5 is effectively suppressed. Further, the water to be treated supplied to the electrolytic cell 2 is treated in the same manner as in the case of FIG. 1 to decompose the phenol extracted substances.

FIG. 3 shows another example of a bipolar fixed bed electrolytic cell that can be used in the present invention.

A mesoche-shaped power feeding anode 13 and a power feeding cathode 14 are provided near the upper and lower ends of the cylindrical electrolytic cell body 12 having flanges 1) on the upper and lower sides, respectively. The electrolytic cell body 12 is preferably made of an electrically insulating material, particularly a synthetic resin, which can withstand long-term use or repeated use.

Between the two power supply electrodes 13 and 14, there are a large number of fixed bed forming particles 15 made of a conductive material such as a carbon material, and a smaller number of insulating particles 18 made of synthetic resin, for example, than the fixed bed forming particles 15. are almost evenly mixed. The insulating particles 18 have a function of preventing the power feeding anode 13 and the power feeding cathode 14 from being completely short-circuited.

When electricity is supplied to the electrolytic cell having such a structure while supplying water to be treated from below as shown by the arrow, each fixed bed forming particle 15 becomes negative on the power feeding anode 13 side and negative on the power feeding cathode 14 side. It functions as a three-dimensional electrode with positive polarization and a large surface area, and in the same way as the electrolytic cells shown in Figs. taken out.

FIG. 4 illustrates a monopolar fixed bed electrolytic cell that can be used in the present invention.

A mesoche-shaped power feeding anode 23 and a power feeding cathode 24 are provided near the upper and lower ends of the cylindrical electrolytic cell body 22 having flanges 21 on the top and bottom, respectively. The electrolytic cell body 22 is preferably made of an electrically insulating material, particularly a synthetic resin, which can withstand long-term use or repeated use.

Between the two power feeding electrodes 23 and 24, a pair of fixed beds 25 made of conductive material, such as carbon fiber, formed into a felt shape are filled in the anode chamber and the cathode chamber with a diaphragm 26 in between. The felt carbon fibers in the room are electrically connected to the power feeding anode 23 and the power feeding cathode 24, respectively, and the fixed bed in the anode chamber is positively charged and the fixed bed in the cathode chamber is negatively charged.

When electricity is supplied to this electrolytic cell while supplying water to be treated from below as shown by the arrow, the fixed bed 25 functions as a three-dimensional electrode with a large surface area, as in the case of Figs. 1 to 3. The phenol extracted substances in the water to be treated are decomposed and taken out from above the electrolytic cell.

(Example) Next, an example of the electrochemical treatment method for water to be treated according to the present invention will be described, but the present invention is not limited to this example.

The electrolytic cell shown in Figure 1, which is made of transparent hard polyvinyl chloride resin and has a cylindrical shape with a flange and a height of 100 mm and an inner diameter of 50 mm, was installed together with a pump in close proximity to a household bathtub. . Inside the electrolytic cell, a diameter 50a+m made of carbon fiber,
5 fixed beds with a thickness of 10 + wm, with an opening ratio of 80% and a diameter of 5
It is sandwiched between 6 polyethylene resin diaphragms with a weight and thickness of 1 and 2a++s, and the diaphragms at both the upper and lower ends are made of titanium with a platinum coating on their surfaces, and have a diameter of 48IIua.
A mesoche-like power feeding anode and a cathode having a thickness of 1.0 mm were placed in contact with each other.

Bath water at 41° C. was supplied to the electrolytic cell at a rate of 51) minutes, and the electrolytic voltage shown in Table 1 was applied between the power supply electrodes to perform electrochemical treatment of the bath water. Table 1 summarizes the presence or absence of generated gas as determined by visual observation during the treatment operation, the amount of phenol extractable substances in the bath water before and after passing through the electrolytic bath, and the power consumption.

As is clear from Table 1, the three-dimensional electrode electrolytic cell can decompose and remove phenol extracted substances, and when the electrolytic potential is less than +0.2V, there is almost no decomposition effect;
．． If it exceeds 2■, the power consumption becomes too large and it is uneconomical.

(Effects of the Invention) Table 1 The method of the present invention is a method in which water to be treated containing a phenol extract is supplied to a fixed bed type three-dimensional electrode electrolytic cell, and the water to be treated is electrochemically treated ( Claim 1).

The water to be treated, such as bath water, which is the object of the present invention, contains oily dispersed substances such as human body grime, that is, phenol extracted substances.

When the water to be treated is supplied to a fixed bed type three-dimensional electrode electrolytic cell, the phenol extracted substance in the water to be treated is transferred to an electrode given a potential, particularly an anode, or an anodically polarized part of a dielectric material or particles for forming a fixed bed. Upon contact, their surfaces undergo a strong oxidation reaction or are exposed to a high-potential electric current, and at least a portion of the phenol extract is decomposed into carbon dioxide and water and removed.

In the method of the present invention, it is not enough that the phenol extract in the water to be treated contacts the voltage application part, and it is necessary to apply a voltage necessary for decomposing the phenol extract between the two electrodes. However, it is not preferable to increase the potential higher than necessary because it leads to power wastage. Therefore, in the method of the present invention, it is desirable to set the anode potential to 20.2 to +1.2 V (vs. 5 CE), which is necessary and sufficient for decomposing the phenol extract material (Claim 2).

In the method of the present invention, a fixed bed type three-dimensional electrode electrolytic cell having a three-dimensional electrode with a large surface area is used, so the water to be treated comes into sufficient contact with the three-dimensional electrode, and the phenol extractables are efficiently decomposed. However, if a bipolar fixed bed type three-dimensional electrode electrolytic cell having a particularly large surface area among three-dimensional electrodes is used (claim 3), the processing efficiency will be further improved.

Graphite, carbon-based materials, activated carbon, etc. can be used as the material constituting the fixed bed of the fixed bed type three-dimensional electrode electrolytic cell (claim 4), and these materials are relatively inexpensive and have a large surface area. , is effective as a fixed bed used in the method of the present invention.

Further, when a plurality of fixed beds are used (claim 5), the surface area is further increased and the treatment efficiency is improved.

[Brief explanation of drawings]

1, 2, 3, and 4 each illustrate a fixed bed type three-dimensional electrode electrolytic cell that can be used in the method of the present invention. 1... Flange 2... Electrolytic cell body 3... Anode terminal for power supply 4... Cathode terminal for power supply 5... Fixed bed 6... Spacer 7... Insoluble metal material 1)...・Flange 12... Electrolytic cell body 13...
Anode for power supply 14... Cathode for power supply 15. 21. 23. 25. Fixed bed forming particles 18. Insulating particles/flange
22... Electrolytic cell body/anode for power supply 24... Cathode for power supply/fixed bed 26... Diaphragm first

Claims (5)

[Claims] (1) A method for treating water to be treated, comprising supplying water to be treated containing an oily dispersion to a fixed bed type three-dimensional electrode electrolytic cell, and electrochemically treating the water to be treated. (2) The anode potential of the fixed bed three-dimensional electrode electrolytic cell is +0.2
The processing method according to claim 1, wherein the voltage is ˜+1.2V (vs. SHE). (3) Claim 1 or 2, wherein the fixed bed type three-dimensional electrode electrolytic cell is a bipolar fixed bed type three-dimensional electrode electrolytic cell in which the water to be treated flows through a fixed bed that is polarized to an anode and a cathode by applying a voltage. Processing method described in . (4) The treatment method according to any one of claims 1 to 3, wherein the fixed bed of the fixed bed three-dimensional electrode electrolytic cell is made of a material selected from the group consisting of graphite, carbon-based materials, activated carbon, and metals. . (5) The process according to any one of claims 1 to 4, wherein the fixed bed type three-dimensional electrode electrolytic cell is an electrolytic cell in which a plurality of fixed beds polarized into anodes and cathodes are installed between anodes and cathodes for power supply. Method.