JPS5816953B2 - Electrolysis method to remove wastewater pollutants - Google Patents

Description

[Detailed description of the invention] Electrolytic reactions oxidize chemicals on the anode surface.

It has also been used to cause reduction on the surface of the cathode.

For example, cyanide can be oxidized and hexavalent chromium can be reduced by electrolysis. A method of adding chemicals to a wax electrolytic cell to carry out an electrolytic oxidation or reduction reaction can be used for wastewater treatment.

For example, in the treatment of contaminated wastewater, adding sodium chloride to an electrolyte is effective in chlorinating cyanide compounds.

Experiments have been conducted in which harmful or toxic substances such as cyanide compounds are destroyed by electrolysis by adding sodium chloride, and chromium compounds are electrolytically reduced by the addition of ferrous sulfate. It's here.

However, this type of operation had low electrolytic efficiency and required continuous addition of chemicals to the electrolytic cell.

For these reasons, these methods were not generally adopted.

It is known that both cyanide compounds and chromic acid can be adsorbed onto carbon surfaces from aqueous waste liquids using so-called adsorption techniques.

However, this method requires backwashing the carbon with acid or alkali.

After the adsorption bed is completely consumed, the chemicals to be removed will flow into the treated water.

This process therefore has a limit determined by the number of adsorption beds that can be utilized, which varies depending on the type of carbon material.

The necessity of backwashing means that it is uneconomical in any case.

When backwashing a chromic acid-adsorbing material with acid, trivalent chromium is released.

This is because the reduction of chromium takes place through the catalytic action of the carbon surface.

On the other hand, when backwashing is performed with alkali, hexavalent chromium is released.

In this case, trivalent chromium is oxidized on the carbon surface and 6
It will probably be chromium with high valence.

Early studies found, for example, that significant amounts of cyanide or chromic acid could be adsorbed by particles of graphite without electrolysis, thus removing a significant amount of harmful substances from the effluent. It turns out that it can be removed.

The carbon particles in the electrolyte contained in the container or cell act as a polarizing material when an electric current is passed between the cathode and the anode.

That is, the part facing or near the cathode is negatively polarized, and the part near the anode is positively polarized.

In this way, each face of the surface will act as a cathode or an anode depending on which electrode it is near or towards, and the carbon particles will act as the intermediate electrode in this system. .

Therefore, the electrolytic reaction takes place on the surface of the carbon particles, and as a result of the close contact between the electrode and the chemicals in the electrolyte, the surface of the carbon is regenerated and the depletion that would surely occur from the adsorption phenomenon alone can be avoided. can.

This was confirmed through experience, and the following findings were made.

That is, as electrolysis continues, a small amount of carbon is lost from the surface of the particles, leaving a layer with less catalytic activity, reducing the effective active surface area.

In this connection, it has been found that lignite does not exhibit any effect as compared to sintered coal or graphite.

It is important to continuously regenerate or reconstitute the carbon surface and thus eliminate the need for backwashing.

This is because the efficiency of this material surface tends to be permanently impaired if a backwash operation is used.

In efforts to put the electrolysis method to practical use, the following method was found to be very important.

That is, conductive carbon flakes or carbon particles are interspersed with non-conductive material, thus making the flow tortuous and particularly passing through the mass of the filler, thereby reducing the amount of carbon generated within the body of the electrolyte. The gas moves along the tortuous path to best exert a natural cleaning or washing action on the carbon material and to continuously maintain its surface in a completely reactive state.

To achieve this, saddle-shaped pieces or particles made of a suitable non-conductive material, such as a resin, ceramic material or glass material, are used, in particular to minimize contact between the conductive particles or masses. In addition, a shape that maximizes the cleaning path by the flow of gas generated at the working electrode is effective.

The term working electrode refers to the electrode from which reaction products or gases that are useful in the method are generated, and the term counter electrode refers to the electrode that is useful for the method if it enters the body of the electrolyte. It refers to anything that produces waste or undesirable products or gases that can be harmful.

The most suitable non-conductive material used for this purpose is a saddle type element conventionally used in glass scrubbers (gas scrubbers).

These elements are zodonut-shaped and made of a soft, porous resin or plastic that wraps around a hoop connected to a central perforated ring.

However, paddle-shaped, mesh, thread-like and other shapes have also been used with success.

The realization that it is important to use non-conductive separation elements with non-metallic conductive materials, either layered or grouped, facilitates the continuous use and reuse of conductive catalytic materials in electrolytic cells. This was an important concept that made it possible.

However, the need to add a certain amount of reactive chemicals was not met with this method.

As a next step, the reactive chemicals or pre-compounds used to regenerate the waste treatment cleaning solution, i.e. to detoxify toxic or harmful dissolved substances therein, may themselves be reconstituted. A method using an electrolytic cell was discovered and defined.

The method can thus be carried out continuously,
The contaminated washing water was sufficiently recycled and recycled for reuse.

In this connection it has been found that porous or permeable walls or enclosures should be provided to isolate the counterelectrodes in the container or cell from which undesired gases are evolved.

For example, if the counter electrode is an anode, as in the case of a reducing solution that generates hydrogen, an enclosure is provided around it to prevent the hydrogen generated at the cathode from reacting with the gas generated at the counter electrode (anode). .

If this measure is not taken, the generator gas generated at the counter electrode will normally react with the gas generated at the working electrode (the cathode in this example) due to its high reactivity, resulting in the desired concentration in the electrolyte. There is a tendency to cause undesirable reactions.

By using a permeable enclosure or separator wall or cup, such generator gas is allowed to exit directly from the electrolyte portion of the enclosure where the electrode is located, eliminating the need for porous It is unlikely that the electrolyte will enter the electrolyte body through the walls and disturb the desired reaction.

It has been found that by using such a control method, all the desired results can be achieved, namely that the conductive material of the auxiliary electrode is always maintained in a fully contacting and effective state.

This allows the reactive chemicals in the electrolyte to be recycled even when they are being chemically reacted or decomposed to detoxify harmful substances or chemicals in the effluent. It is now possible to configure.

Furthermore, it has been found that this operation can be carried out sufficiently continuously, that the aqueous cleaning solution can be circulated to the reaction, and that there is little wear and tear on the chemical components of the electrolytic cell. Any wear and tear is limited to a small portion of the circulating chemical cleaning solution remaining on the surface of the component being cleaned and transferred, for example, to the next wash bath.

Not only is the above objective achieved by using non-conductive so-called spacers in the filling mass, but also
It is possible to prevent clogging of the electrolyte bed and coating of the surface of the auxiliary electrode with an insoluble precipitate layer.

A typical method of operation for carrying out the invention will now be described with reference to the drawings.

In the figure, reconstituted aqueous cleaning fluid is removed from electrolytic cell D and then enters reservoir or tank E.

This is called a holding tank in which the sediment is deposited and removed from there.

According to the figure, wash water is continuously circulated between the process wash tank A and the electrolytic cell or tank E, with storage tank E being utilized for appropriate conditioning.

In the illustrated example, A is a metal strip 10 that is raining a treatment tank or treatment bath, for example a metal strip 10 that is being continuously moved forward.
such as cyanide, chromic acid or nitrite surface treatment baths for parts shown in

As shown, strip 10 exits a processing or conditioning tank A and enters a wash tank B.

In tank B, a solution, particularly an aqueous solution, is continuously flowed over the surface of the component to clean any residues of toxic or harmful compounds from tank A.

This residue is often a metal cyanide, a metal nitrite, or a metal oxide such as chromium oxide.

The cleaning liquid is introduced into the vessel or tank B through the line 11, where it dissolves impurities before exiting through the outlet 13 and returning through the return arrangement 14.

The component 10 then passes through a rinsing tank C. Here, there are very few, if any, toxic chemicals to be cleaned, mainly entrained or residual substances from the aqueous solution of B.
If necessary, the water may be collected into the drain pipe 16 via the overflow part 15.

The contaminated aqueous cleaning fluid exiting from distribution W14 contains toxic substances or chemicals that must be removed in electrolytic vessel or cell D.

As shown, cell D has a pair of spaced apart electrodes 25 and 26.

Depending on whether the operation is a reduction or oxidation operation, electrodes 25 and 26 are cathodes or anodes.

For example, if the operation is a reduction operation where hydrogen is generated at the cathode, the anode becomes the counter electrode from which the waste gas is generated and is therefore surrounded, separated and wrapped in a permeable or porous wall or cup 27. The electrode 25 that is located on the ground becomes the anode.

In this example, electrode 26 becomes the cathode.

On the other hand, when the operation is an oxidation operation and oxygen is generated from the anode surface, the counter electrode 25 becomes a cathode and the electrode 26 becomes an anode.

In connection with this. Electrical terminal 2 for direct current power flow
The polarity of 0 and 21 is reversed as required.

Electrodes 25 and 26 are made of a suitable material, and may be made of graphite.

In the illustrated system, non-metallic conductive material 30, such as small pieces of compressed carbon, are interspersed within the body of electrolyte in cell D, and further separated by non-conductive elements 31, such as resin material, to form a packing mass. are doing.

In the illustrated system, the oxidizing or reducing pre-chemicals used within the cell are reconstituted when used to destroy hazardous substances.

This system is very efficient and economical in its operation.

This is because the electrical energy can sufficiently and continuously maintain the surface condition of the conductive material 30 in a valid and clean state, yet the preliminary or reactive chemicals can be continuously used and reconstituted. It is from.

In this way, it becomes possible to continuously circulate and use the aqueous cleaning liquid.

The regenerated cleaning liquid flows into the storage tank E through the overflow part 32 and the pipe 33, and by using this storage tank, deposits can be removed, and the stored liquid can be removed by using, for example, an electric pump P. It is easily circulated through the piping 11.

The sediment is removed from time to time by opening the storage tank door 34.

Next, some examples of wastewater treatment are shown.

Among these, the methods indicated by the numbers ■ and ■ are two methods of implementation according to the present invention, and have resulted in significant improvements.

Regeneration of the aqueous cleaning liquid containing metal cyanide chromic acid or nitrite ions takes place.

Cyanide compound■ CN- is adsorbed and removed by carbon particles, and the waste liquid is 2
Passed through cell 1.

Average 60■/hour. The first 5 hours of operation were 247 .mu./hour.

After 63 hours, the removal rate was 0.

II Aeration was carried out rapidly in order to adsorb and remove CN- and regenerate the carbon surface with oxygen.

Average 74, 1 m9/hour.

The first two hours of operation were 252 m9/hr.

After 10 hours, the removal rate was X'O.

Using an electrolyte containing m NaCl) 209/IJ,
The cathode was wrapped in a thin film, but no graphite or carbon intermediate electrode was placed in the cell, and the CN- was removed by electrolytic oxidation.

The average removal rate was 192 mV'Ampere-hours.

After 63 hours of operation, the removal rate remained nearly constant at 192~/Amp-hour.

(2) In a cell containing a graphite intermediate electrode, however, CN- was removed by electrolytic oxidation without adding NaCl or enclosing the cathode.

The average removal rate was 44~/Amp-hour.

After 21 hours of operation, the current was constant at 34.5 η/amp-hour.

■ In a cell containing a graphite intermediate electrode, Na(J?30 &/lj) was added to the electrolyte to electrolytically oxidize and remove the CN-, but without wrapping the cathode with a thin film.

The removal rate was 847 m9/amp-hour and remained constant at 84 m9/amp-hour after 60 hours of operation.

(2) CN- was removed by electrolytic oxidation using an electrolytic cell according to the present invention.

Using a graphite intermediate anode, NaCl20.9/A
was added and the cathode was wrapped in a thin film.

Removal rates averaged 389~/Ampere-hour.

After 28 hours of operation it remained constant at 3897'n41/amp-hour.

(2) CN- was removed by electrolytic oxidation using an electrolytic cell according to the present invention.

Using graphite intermediate anode, NaC1120g/
1 was added and the cathode was wrapped in a thin film.

A plastic saddle-shaped element was inserted between the graphite intermediate electrodes to make gas cleaning effective, and the flow of the solution was devised so that the precipitates were washed out of the system.

Removal rates averaged 3207/llp/amp-hour.

After 133 hours of operation, the value remained constant at 320 mg/ampere-hour.

The chemical and electrolytic reactions in this system are explained as follows.

A1. NaCN+2NaOH+C12-+Na
CN0+2N a Cl+I-(20 (chemical reaction) 2,
NaCN+1/202 → NaCN0 (electrolytic reaction) 3,
T-T2O-2e→O+ 2 H+↑ (electrolytic reaction, oxygen generation at the anode) B 2NaCNO+4NaOH+3C4-+6
NaC7+ 2C02+N2+2H20 (chemical reaction) A and B are chemical and electrolytic reactions for oxidizing CN-.

C2Na(J'-2e-+CJ'2+2Na" (electrolytic reaction, C12 generated at the anode) This formula describes the electrolytic regeneration reaction of t-IJium chloride.

Chromic acid ring formation (1) Adsorption ring formation of CrO3 using carbon particles was carried out, and the waste liquid was passed through 21 cells.

Average 1.88■/hour. 2.8 for the first 11 hours of operation
It was 37n9/hour.

After 30 hours of operation, the ring element ratio was approximately O.

■ No aeration test was performed.

Electrolytic ring formation of CrOs was carried out using an electrolyte containing NFeSO410&/l.

The anode was wrapped in a thin film, however there was no graphite or carbon intermediate electrode in the cell.

The average reduction rate was 145 Tn9/Ampere-hour.

The first two hours of operation were 5.24~/Amp-hour.

After 12 hours of operation, a nearly constant value of 1.45 m9/T ampere-hour was obtained.

■ Cr in an electrolytic cell containing a graphite intermediate electrode
Perform electrolytic oxidation of O3.

However, no ferrous sulfate was added and the anode was not wrapped.

The average ring rate is Q, 851n9/ampere-hour.

During the first 23 hours of operation it was 3.45 m9/amp hour.

After 60 hours of operation, the ring rate remained constant at 0.35 .mu./ampere-hour.

■ Using an electrolytic cell containing a graphite intermediate electrode,
Ferrous sulfate was added to electrolytically reduce CrO3.

However, the anode was not wrapped in a thin film.

(2) Crys was electrolytically reduced using the electrolytic cell according to the present invention.

A graphite intermediate electrode was used, 10 g/l of ferrous sulfate was added, and the anode was wrapped in a thin film.

The average reduction rate was 6.547 n9/Ampere-hour.

(2) Cr 03 was electrolytically reduced using the electrolytic cell according to the present invention.

A carbon intermediate electrode was used, a plastic saddle element was inserted, and the anode was wrapped in a thin film.

The average ring rate was constant at 3.631 n9/ampere-hour.

Even after 300 hours, the power was 3.63 mp/amp-hour.

The chemical and electrolytic reactions in this system are explained as follows.

A 1.2Cr03+6FeSO4+6H2SO4→
Cr2(SO4)3+3Fe2(SO4)3+6Hρ2
, Cr 03 +3 e −+Cr 203 or Cr”+ 3 e −+cr3+ (ring element) These are chemical and electrolytic reactions for ringing hexavalent chromium to trivalent chromium.

B' L 6Fe""+6e-+6Fc++ (second
(iron to ferrous iron) 2°3H20-6 These reactions involve the regeneration of reactive chemicals by electrolytic action.

Another important electrolytic oxidation reaction is the oxidation of nitrite ions to nitrate ions.

This is because nitrite ions are toxic to sentinel mammals.

Nitrite ions are oxidized in the electrolytic cell at neutral or acidic pH (8 or less) as described above.

The liquid contains sulfur chloride as a pre-oxidant to trigger the chemical reaction.

This chemical reaction is explained as follows.

A1. NaNO2+C12+H20→NaNO3+
2HCl (chemical reaction) 2, NaN0 □ + 1/20 □ - + NaN03 (solution window) These cause chemical oxidation or electrolytic oxidation of nitrite.

B1. 2Na(J'-2e-+CI!, 2+2
Na+ (electrolytic reaction) 2, H2O2e→O-2+2H
(Electrolytic reaction) These regenerate chlorine by oxidizing chloride through electrolytic reaction.

During this anodic reaction, the cathode is separated from the body of the electrolyte by a porous or permeable thin wall membrane.

Although these reactions illustrate embodiments of the invention, depending on the type of reaction required, treatment or pre-chemicals may be added initially, such as t-IJium chloride or ferrous sulfate. .

The spacing element 31 is made of a suitable resin or plastic, such as polyvinyl chloride, and the permeable wall 27 is made of a resin or ceramic material.

The method of the present invention is not only very effective and economical from the point of view of the recovery of used and reused chemicals, but also from an environmental science point of view, as it avoids discharging toxic waste into the sewage system. appropriate and excellent.

In the conventional method using chlorine as a chemical substance, l-IJium chloride is emitted.

This is because the cyanide reaction leads to cyclization of chlorine, which is neutralized by alkaline sodium or calcium compounds.

Thus, 5.97/9 sodium chloride will be excreted per kg of sodium cyanide.

Similarly, in the usual chemical disposal of chromium, sulfuric acid
Iron is excreted, in this case Fe2 (
804) 3 will be ejected as well as 9 on 8.4.3.

In normal chemical treatment of sodium nitrite, when chlorine is used, hydrochloric acid is emitted.
per HCll. 06kg is discharged.

On the other hand, as mentioned above, in the treatment using the circulating bath of the present invention, the wear and tear of the treatment chemicals is almost negligible or greatly reduced.

The treatment chemicals are retained within the system and the only loss of chemicals released into the environment is due to entrainment or residue on the surfaces of component 10 as it moves from tank B to tank C. be.

The solid conductive filler material 30 is preferably made of a non-metallic material such as carbon, preferably compression molded, and has a suitable shape with a large exposed surface area.

If a rectangular, square or cylindrical shape has a uniform shape, its dimensions are approximately 1/4 to 1/4 across.
Conveniently, the length is in the range of 3 inches and the length is in the range of about 1 to 6 inches.

The solid non-conductive filling element 31 may be made of a suitable resin, glass, etc., and may have any suitable shape, but it is particularly suitable for gases that have a winding path in which the flow and cleaning movement within the electrolyte body is large. It is preferable that the value is the maximum.

In the present invention, the preliminary chemical is continuously regenerated in the electrolytic cell or tank D, whether it is an oxidizing substance or a cyclic substance (oxidant or cyclic agent). .

As an example, when the cell is used as an oxidation cell, the cyclic gas, compound or component that forms in the cathode (counter electrode) zone is surrounded by a permeable wall.

In this way, cyclic compounds are prevented from reversing the oxidation reaction.

The permeable (porous, semipermeable or neutral membrane) wall is characterized by allowing the movement of electrons and the passage of ions, but not the passage of generator hydrogen.

Therefore, thin membranes such as semipermeable membranes can exclude hydrogen gas.

A semipermeable membrane may be used that only allows positively charged cations to migrate toward the cathode.

Typical materials used for this purpose are sulfonated threnes or resins, which have an ionic resin structure capable of accepting and exchanging cations.

If a porous material is used, it is best to use a thin film such as a ceramic or plastic material or cellulose acetate that is dense enough to allow only the movement of electrons but not the ionized salts. suitable.

To keep the solution fully regenerated, a portion of the solution being processed is constantly recycled and only a small amount of reactive chemicals are added as needed.

The system operates by continuously regenerating the process solution waste, such as by supplementing the sodium chloride oxidizer as needed to increase the initially added material by a small amount.

The application of the method of the invention is not limited to the treatment of toxic or hazardous waste treatment solutions as shown in the drawings.

That is, it can also be used to detoxify other toxic or hazardous gases or substances dissolved in liquids.

For example, substances such as mustard gas (yperite) can be oxidized to sulfoxides to yield derivatives useful as chemical intermediates for making pesticides.

By dissolving this harmful gas in a common organic solvent or ether, mixing it with water, adding an emulsifier, and then electrolyzing it, the harmful substance is converted into, for example, β,I dichlorodiethyl sulfoxide. Ru.

The sulfoxides are water soluble and are removed by circulating flow from the processing vessel and recovered by suitable means such as phase separation or solvent extraction.

In a similar bed process, methylhydroxyl, ethylhydroxylamine or isopropylhydroxylamine can be converted to nitromethane, nitroethane or 2-nitropropane.

Thus, by using the method of the invention, contaminants are destroyed in a relatively simple manner, while oxidizing or cyclic agents that promote undesirable and adverse reactions or inhibit desired reactions are sequestered. As a result, harmful substances in the solution are sufficiently removed and harmless substances are produced.

Continuous regeneration of hazardous or pollutant treatment solutions was achieved.

Next, the embodiments of the present invention are enumerated as follows.

■ By inserting a permeable wall into the electrolyte and placing it spaced around the counter electrode to isolate it from the electrolyte body, undesirable reaction products generated at the counter electrode can be removed from the electrolyte. A method as claimed in the claims for preventing entry into the body.

2. The method of embodiment 1, wherein the permeable wall is comprised of a material selected from the group consisting of porous ceramic materials, permeable resins, semipermeable membranes, and neutral membranes.

3. The method as claimed in the claims, in which the surface of the conductive element is maintained in a highly adsorbent state by cleaning with gas generated in the electrolyte body.

4. Embodiment 3 in which the conductive elements are separated from each other and the path of the gas flowing through them is made winding by using non-conductive solid filling elements in the nursery school.
The method described in section.

5. A resin saddle type element is used as a non-conductive element, a solid carbonaceous material is used as a conductive filling material, and a non-conductive element is used to minimize contact between the conductive elements. Embodiment 4. Method according to embodiment 4.

6. A conductive element made of solid carbonaceous material with a diameter of 1/4 to 3 inches and a length of 1 to 6 inches is used, and a non-conductive element made of a fairly soft resin material is uniformly dispersed in an electrolytic solution. 5. The method of embodiment 4, wherein the method is used in contact with a conductive element in the body.

7. A patent claim in which the treated waste solution is removed from the electrolyte body and reused to dissolve and remove harmful substances, and then this waste solution is treated and circulated in the electrolytic cell with the above-mentioned bank. How to describe the range.

8. The method of embodiment 7, wherein the pre-compound is continuously reconstituted in the cell in said treatment.

9. Has a ring-forming effect on harmful substances as a preliminary compound,
Moreover, the method according to the claims, wherein a substance that generates hydrogen gas at the cathode is used as the desired product produced by the electrolytic reaction.

10. Using an oxidizing pre-compound to react with a hazardous substance and generating generator oxygen at the anode as the desired product by electrolytic reaction (method as claimed in the claims).

11. The method according to embodiment 9, wherein ferrous sulfate is used as a pre-compound and the hazardous substance is chromic acid.

12. Using an alkali metal chloride as a preliminary compound,
Embodiment 1 where the hazardous substance is a metal cyanide
The method described in item 0.

13. The method according to the claims, wherein the harmful substance is one of the group consisting of amine nitrite and metal nitrite, and an alkali metal chloride is used as a coexisting compound.

14. In an electrolytic cell for converting and rendering harmful substances dissolved in leakage of aqueous waste liquid, an electrolyte storage container having at least one pair of separated anode and cathode is used, and one electrode of the electrolyte storage container is used. is the working electrode and the other is the counter electrode, and a permeable wall is provided around the counter electrode to isolate a portion of the electrolyte and the reaction products generated at the counter electrode from the working electrode and the body of the electrolyte in the container. Moreover, the layer filled between the electrodes in the electrolytic solution is made of a mixed group of solid conductive nonmetallic elements and nonconductive spaced apart resin elements,
A renewable electrolytic cell in which the resin element creates a winding path for gas flowing through the electrolyte body.

15. The electrolytic cell according to embodiment 14, wherein the permeable wall is a semipermeable membrane.

16. The electrolytic cell according to embodiment 1, wherein the permeable wall is a neutral thin film that allows both cations and anions to pass through.

[Brief explanation of drawings]

Teeth are electrolyzed for aqueous cleaning solution treatment, which is an example of the implementation of the present invention↓
1 is a cross-sectional view of the system; In this figure, A is a processing tank or processing bath, B is a washing tank, C is a washing tank, D is a cell, E is a storage tank, P is an electric pump, 10 is a metal strip, 11 is piping, and 12 is an electric pump. (2P), 13 is an outlet, 14 is a transportation pipe, 15 is an overflow part, 16 is a drain pipe, 25 and 26 are spaced opposing electrodes,
27 is a cup, 20 and 21 are electric terminals, 30 is a non-metallic conductive material, 31 is a non-conductive element, 32 is an overflow part, 33 is a pipe, and 33 is a door of storage tank E.

Claims (1)

[Claims] In an electrolytic method for removing pollutants dissolved in an aqueous waste solution in an electrolysis cell having at least one pair of spaced apart anodes and cathodes, one working electrode and the other a counter electrode, and an electrolyte, the electrolyte is A pre-compound to be dissolved, a separate charge of conductive carbon and/or graphite, and a non-conductive material are contained in the cell, and a current is passed through the electrolyte between the electrodes to convert the conductive element into a bipolar element. The gases generated in the electrolyte are activated to clean the surface of the conductive element by passing the gases generated in the electrolyte in a tortuous passage through the interstices between the fillers, thereby removing the electrolytic reaction products of the pre-compound and the gaseous formation of the electrolytic reaction. reacts with contaminants in the waste solution to form harmless substances, thereby generating desired reaction products at the working electrode of the force pair and preventing gaseous reaction products generated at the counter electrode from entering the electrolyte. An electrolytic method for removing wastewater pollutants, which consists of various steps.