KR860000736B1 - Electrode material - Google Patents

Abstract

An electrode material consists of particles of diam. 0.3 - 25 mm which are either coated partially or totally with a mixt. of hydrophobic binding agent and electroconductive catalyst, or bound with frozen liquid mixt. of the prescribed materials. An electrolytic bath comprises anode and cathode with their own compartments, aq. electrolytic soln. supply, elecric device, and product withdrawing device. At least one of the electrodes are of the prescribed electrode material.

Description

Electrode composition and preparation method thereof

The present invention relates to an improved electrode composition and a method of making the same.

Chlorine and alkali metal hydroxides (eg sodium hydroxide and potassium hydroxide) are produced commercially by electrolysis of the corresponding alkali metal chloride saline in the electrolytic cell. In in this type of electrolytic cell the anode which the anode is separated from the cathode by an ion permeable diaphragm the following _{^{reaction: 2Cl - → Cl 2 + 2e}} - and the chlorine is produced by, in the negative electrode and the hydrogen is absorbed on the negative electrode surface, the hydroxyl group is generated by the ^{hydrogen-molecules} are desorbed from the negative electrode goeneun practical multistage reaction ^{_{2H 2 O + 2e - → H}} 2 + 2OH.

The total hydrogen reaction is a series of hypothesized adsorption and desorption reactions that consumes about 0.8 volts in an alkaline solution and the oxygen reduction reaction theoretically produces 0.4 volts, so that the cathode in the chlorine bath is desorbed with oxygen instead of releasing hydrogen. In this case a saving of about 1.2 volts is possible. Cathodes already developed for the use of oxygen as depolarizers are characterized by a thin sandwich structure of a microporous plastic separator combined with a catalyzed layer pressurized on a wire screen current collector, for example, treated with polytetrafluoroethylene. do. In the prior art depolarized cathode, oxygen is injected into the catalyst stage through a microporous support. These cathodes exhibit their functions but have various drawbacks such as separation or separation of each layer and flooding of the microporous layer.

The present invention relates to an electrode composition comprising a substrate at least partially coated with a mixture of a binder and an electrochemically active electroconductive catalyst, wherein the electrode composition is coated particles having an average diameter of 0.3 mm to 2.5 cm. .

The present invention also forms a fluid mixture of an electrochemically active electrically conductive catalyst and a binder, solidifies the fluid mixture to bind the catalyst to the substrate and to form the electrode composition into particles having an average diameter of 0.3 mm to 2.5 cm. It is characterized by a method of producing an electrode composition.

The invention also comprises an electrode composition comprising feeding an aqueous electrolyte into an electrolytic cell and comprising an anode and a cathode, wherein at least one of these electrodes is at least partially coated with an electrically conductive mixture of a hydrophobic material and one or more catalysts, The electrode composition consists of a plurality of coated particles each having an average diameter of 0.3 mm to 2.5 cm), and the electrolytic product is recovered, so that the weak liquid electrolyte chamber having the positive electrode and the negative electrode A method for electrolyzing an aqueous electrolyte solution in an electrolytic cell comprising a catholyte electrolyte chamber.

The invention also relates to an anolyte electrolytic chamber with a positive electrode, a catholyte electrolytic chamber with a negative electrode, an apparatus for supplying an aqueous electrolyte solution to an electrolyzer, a positive electrode and a negative electrode (where at least one of these positive and negative electrodes is a hydrophobic material and at least one catalyst) Consisting of an electrode composition consisting of a substrate partially coated with an electroconductive mixture of and an electrode composition comprising a plurality of coated particles each having an average diameter of 0.3 mm to 2.5 cm). An electrolytic cell comprising a device for recovering an electrolysis product.

The electrolytic cell of the present invention may optionally contain an ion permeable diaphragm located between the anode and the cathode, and, if necessary, may contain a device for supplying a gas to the electrode. Layers of these particles have been found to be useful as gas electrodes and they can be used as anodes or cathodes.

The substrate to be coated must be a material that can retain its shape. In order to conveniently prepare the above-mentioned particles, it is preferable that the substrate hardly deforms when the substrate is heated at a temperature of 350 to 375 ° C. for 1 hour.

The substrate may be a sintered fluorine, a solid material or a bound aggregate of small particles. Suitable construction materials include, but are not limited to, steel, iron, graphite, nickel, platinum, copper and silver. Of these, graphite is particularly preferred because of its usefulness and low cost. The substrate may be the same or different in composition from the coating.

The substrate may be electrically conductive or non-conductive. An electrically conductive substrate is preferred because of its smaller resistance to the flow of electrical energy through the particles. Non-conductive substrates can also be used because at least in part the coating with an electrically conductive coating creates a flow path for current. However, nonconductive substrates exhibit greater resistance because charge must flow around the particles through the coating of the nonconductive substrate rather than through the particles.

The average diameter of the particles is 0.3 mm to 2.5 cm. When used as an electrode composition, it is generally preferred to use particles smaller than 2.5 cm. This maximizes the surface area and increases the high porosity in the layer of particles. Particularly preferred are particles of 0.7 mm to 4 mm in size when the particles are used as the electrode composition. Particles less than 0.3 mm tend to fill gaps and provide high resistance to fluid flow through the particle layer. Particularly preferred are particles of 0.7 mm to 4 mm in size when the particles are used as the electrode composition. Particles less than 0.3 mm tend to fill gaps and provide high resistance to fluid flow through the particle layer. Substrates with particle sizes greater than 2.5 cm are undesirable because they minimize the surface area at which electrochemical reactions can occur.

The particles may be used in any form, and irregularly shaped particles may be conveniently used, but spherical particles are preferred because they form a layer having an optimum porosity and surface area. Irregularly shaped particles tend to fill gaps to minimize the porosity of the layer.

The substrate need not be chemically inert with respect to the electrolyte or electrolytic product of the process of the invention in which the particles are used. However, it is desirable that the substrate be chemically inert so that the substrate does not need to be entirely coated. If the substrate is not chemically inert, the coating applied to the substrate should be a complete coating that prevents a reaction between the substrate and the electrolyte or electrolytic product.

The coating on the substrate is a mixture of a binder and an electrochemically active electrically conductive catalyst. The binder must be a substance that can be injected into the fluid form by melting, dispersion or dissolution. The binder must be chemically stable to the electrolyte or product to be contacted when used in the electrolyzer. The binder must be stable to the operating temperature of the electrolyzer to be used. The binder itself does not necessarily need to be electrically conductive because the catalyst mixed with it is electrically conductive. The coating may be a porous coating or a nonporous coating, depending on the composition of the substrate. The coating may be a porous coating when the substrate is chemically inert with respect to the electrolyte. However, if the substrate is not chemically inert to the electrolyte, the coating must be nonporous to prevent reaction between the substrate and the electrolyte or the electrolytic product.

The binder is preferably a hydrophobic material. The hydrophobic binder, when used as an electrode composition, can create bubbles on the particle surface by the hydrophobic binder, resulting in a maximum low moisture between the gas and the liquid. If the binder is not hydrophobic, the surface of the particles may be wet and no bubbles may be generated at all.

Various hydrophobic substances can be used as the binder. Hydrophobic materials include polyfluorofluoro hydrocarbons such as polytetrafluoroethylene, polychlorotrifluoroethylene, polytrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride and tetrafluoro ethylene, trifluoroethylene , Interpolymers and terpolymers containing chlorotrifluoroethylene, vinylidene fluoride and vinyl fluoride), among which polytetrafluoroethylene is particularly preferred.

The particles in the coating also contain an electrochemically active electrically conductive catalyst. The choice of catalyst depends on the type of method for preparing the electrode composition. Examples of these methods include oxygen reduction and hydrogen oxidation. Preferred catalysts for the oxygenation of oxygen include materials such as carbon black, platinum, silver and activated carbon. Carbon-black is particularly preferred because of its excellent physical properties and its usefulness. Carbon black having a surface area of 100 to 1000 m 2 per gram of catalyst is preferred. Carbon-black having a surface area of 150 to 500 m 2 per gram of catalyst is particularly preferred.

The substrate may be partially or wholly covered with the binder catalyst mixture. It is desirable to cover almost the entire surface of the particles. The coating may be of any convenient thickness. Particularly preferred is a thickness of about 1 mm. This coating provides sufficient coating to cover almost the entire surface of the particles, but is thin enough to preserve the catalyst-binder mixture needed to coat the particles. If the thickness is in excess of 5 to 6 mils, it is uneconomical in that a substantial portion of the catalyst is covered by the additional catalyst and the binder and thus cannot be used for the reaction.

The coating may contain a peroxide decomposition catalyst. In view of this, the peroxide decomposition catalyst can be coated on both surfaces on the outer surface as well as on the inner surface of the particles. Particles coated with a peroxide decomposition catalyst on the outer surface of the substrate are preferred because the unexposed catalyst becomes ineffective and the catalyst is not preburned.

Peroxide decomposition catalysts are known in the art, and representative ones are transition metals having hydrogen adsorption properties. Preferred peroxide decomposition catalysts include copper, silver, platinum, gold and mixtures or compounds thereof. Particular preference is given to mixtures or compounds thereof in admixture with silver, platinum and carbon black.

Another particularly preferred type of known peroxide decomposition catalysts is (1) alkali metals, alkaline earth metals and group II B metals and (2) transition metal compounds, which also have electrocatalytic properties or surface It is characterized by catalytic properties. Of these, ash titanium stone is particularly preferred.

The scope of the present invention also includes a method for preparing coated particles suitable for use as electrode composition. Coated particles are prepared by forming a fluid mixture with a particulate substrate, an electrochemically active electrically conductive catalyst and a binder. Solidifying the fluid mixture binds the catalyst to the substrate. In this way, particles having a substrate at least partially coated with a binder and a catalyst are formed.

When the particulate substrate is mixed with the catalyst and binder, a fluid mixture is first formed. This mixture can be fluidized in one of several ways. The binder itself may be heated to the temperature of the softening or melting point of the binder. The binder may soften or melt prior to mixing with the catalyst and substrate or upon mixing with the catalyst and substrate. Softening or melting points of various materials suitable as binders are well known to those skilled in the art. These softening or melting points are described in numerous references or chemical handbooks.

A second method of forming the fluid mixture is to disperse the binder, catalyst and substrate in the liquid medium. As the liquid medium, various liquid media which are non-reactive with the aforementioned three components constituting the mixture can be used. As the liquid medium, water or other liquid medium which is not a solvent for any component of the mixture is particularly preferred. As the liquid medium, water or other liquid medium which is not a solvent for any component of the mixture is particularly preferred. After mixing the mixed components, a dispersion may be formed or dispersed in the liquid before any one of the mixed components is mixed with the other components. However, it is important to sufficiently disperse the components in the liquid medium.

A third method of forming the liquid mixture is a method of dissolving the binder in a solvent. The binder dissolved can then be mixed with the catalyst and the substrate. The solvent must be incapable of dissolving neither the substrate nor the catalyst. The binder can be dissolved before or after mixing the components.

After forming the fluid mixture, the fluid mixture is solidified to bind the catalyst to the substrate. This mixture can be solidified by one of several methods. The method of coagulation depends slightly on the method initially used to form the fluid mixture. If the binder is melted or softened to form a fluid mixture, the mixture may only be cooled to solidify the binder. One or more components may be dispersed in the liquid medium to only cool the liquid mixture to coagulate the binder. When one or more components are dispersed in a liquid medium to form a fluid mixture, coagulation can be caused by removing the liquid medium from the mixture. The liquid medium can be removed by heating the mixture to evaporate the liquid medium or by keeping the mixture under vacuum to evaporate the liquid medium. If the binder is dissolved in a solvent to form a liquid mixture, it can be solidified by removing the solvent. . When the binder is dissolved in a solvent to form a liquid mixture, it can be removed by removing the solvent. When the binder is dissolved in a solvent to form a liquid mixture, it can be coagulated by removing the solvent. The solvent may be removed by heating evaporation or vacuum removal or by reacting the solvent with other components.

If necessary, the mixture may be treated to prevent the coated particles from adhering to each other upon solidification to form a single mass. A convenient method for preventing the particles from adhering to each other during the coagulation operation is a stirring method. The number of stirring times and degree is minimized, and the objective can be achieved by only stirring or rolling a composition at the time of solidification. Stirring during solidification improves the uniformity of the coating on the substrate.

If desired, the coated particles may be heated to a temperature above or above the softening point of the binder after solidification to increase the binding strength of the binder to the substrate. Heating to this temperature softens the binder and mixes more and more with the catalyst, resulting in better binding to the substrate.

If necessary, the coating operation of the particles can be repeated several times. In this method, the amount and thickness of the coating can be adjusted according to the number of repeated operations. The thickness of this coating is not critical to the invention.

If desired, surfactants may be added to the fluid mixture to increase the wettability of the substrate and catalyst by the binder. The addition of surfactants results in better contact of the mixture and more even distribution. In addition, it is preferable to use a surfactant in a form that can be removed from the particles after the bonding has occurred. Such surfactants are preferred since the coated particles are preferably not wetted by the electrolytic solution when used in the electrode composition. As described above, bubbles are preferably formed on the surface of the particles. In this regard, since the presence of the surfactant increases the wettability of the particles by the electrolyte solution, the formation of bubbles can be minimized. Preferred surfactants are therefore nonionic surfactants which can be pyrolyzed to leave only carbon residues. Such surfactants are known in the art and need not be described in more detail.

If desired, the particles can be combined and then washed to remove catalyst that is not bound to the substrate. Water and liquids other than solvents for any component of the coating are bonded, water is particularly preferred for convenience.

The weight ratio or volume ratio of catalyst and binder to substrate depends on the degree of coating required on the substrate. If a small amount of coating is desired, only a small amount of catalyst and binder should be mixed with the substrate to form a fluid mixture. In contrast, thick coatings require an increase in the amount of catalyst and binder.

The ratio of the amount of catalyst to the amount of binder can vary widely. For example, when carbon black is used as a catalyst and polytetrafluoroethylene is used as the binder, a weight ratio of 4: 1 to 1: 4 can be used. The ratio of carbon black to PTFE is preferably 1: 1.5 to 1.5: 1 by weight, and other catalysts and binders should be used within the same ratio.

When metal powders such as silver, platinum or other metals are used as the catalyst, it is convenient to express the ratio in volume units instead of weight. The metal powder to binder can be in the range of from 4: 1 to 1: 4 volumes, preferably in a 1: 1.5 to 1.5: 1 volume ratio.

If desired, various types of catalysts can be added to the fluid mixture. One preferred form of the invention includes a method of adding a peroxide decomposition catalyst with a carbon black catalyst. When using these two types of catalyst the peroxide cracking catalyst should be used in the range of 1 to 35% by weight relative to the total catalyst and the carbon black catalyst should be used in the range of 65 to 99% by weight relative to the total catalyst. Preferably, the peroxide decomposition catalyst should be used in the range of 3 to 10% by weight based on the total catalyst, and the carbon black catalyst should be used in the range of 90 to 97% by weight relative to the total catalyst. This catalyst mixture should be used in the above ratio ranges in terms of catalyst to binder ratio.

Generally, peroxide decomposition catalysts used in the formation of fluid mixtures are catalyst precursors. In other words, the material used in the fluid mixture is a compound of the catalyst and must be thermally or chemically decomposed to become the catalyst itself. Such thermal or chemical degradation can be achieved at any stage of the process of forming the coated particles. The precursor is preferably thermally or chemically degraded before mixing with the binder and the substrate. In addition to better control of thermal or chemical decomposition of the catalyst precursor, this maximizes the contact between carbon black and the oxidation decomposition catalyst. The two catalysts are mixed and then decomposed before mixing with the substrate and binder to obtain maximum contact between the carbon black and the peroxide decomposition catalyst.

The coated particles described above are suitable for use as electrode materials because of their electrical conductivity and catalytic activity. These coated particles can be conveniently used as a packed layer electrode. In this way, the particles are layered and supported in some convenient way in the electrolyzer. These particles are electrically connected to a power source combined with an electrolyzer. If necessary, a current collector may be used, and the current collector may surround the catalyzed particles and may be a wire mesh bag, a wire mesh container, or the like containing the catalyst particles.

When peroxide decomposition catalysts are contained in the coated particles, these particles can be used in the electrolytic cell to produce hydroxides. If the peroxide decomposition catalyst is not contained among the coated particles, these particles can be used in the electrolytic cell to produce peroxides.

According to a preferred form of the present release method using the aforementioned particles, an aqueous alkali metal halide in an anolyte electrolytic chamber containing an anode and a catholyte electrolytic chamber containing a negative electrode and, if necessary, an electrolytic cell having an ion permeable diaphragm therebetween. Feed the brine. Typically the anode is a valve metal, for example titanium, tantalum, tungsten, cadmium, etc. having an appropriate electrocatalyst surface. Suitable anode electrocatalyst surfaces are well known in the art and are compounds of transition metals, oxides of transition metals, transition metals, in particular compounds of platinum group metals, platinum group metals and compounds of platinum group metals. Of these, compounds of an oxide of the platinum group metal and a valve metal, that is, an oxide such as titanium, tungsten, and cadmium are particularly preferable. The ion permeable diaphragm can be an electrolyte permeable diaphragm, such as a deposited asbestos diaphragm, a preformed asbestos diaphragm, or a microporous synthetic diaphragm. In addition, the ion permeable diaphragm may be ion permeable and electrolyte impermeable as a cation selective ion permeable membrane. Typically cation selective ion permeable membranes are pullouro hydrocarbon polymers with hanging acid groups. Typical merdaline acid groups include sunonic acid groups, carboxylic acid groups, phosphonic acid groups, phosphoric acid groups, their precursors and their reaction products.

The anolyte is typically an aqueous brine containing 120-250 g of sodium chloride per liter or 180-370 g of potassium chloride per liter, typically having a pH of 1.5-5.5. Brine feeds are typically saturated or nearly brine saline containing 300-325 g of sodium chloride per liter or 450-500 g of potassium chloride per liter. The catholyte electrolyte recovered from the electrolytic cell contains about 10 to 12% by weight of sodium hydroxide 15 to 25% by weight of sodium hydroxide, or about 15 to 20% by weight of potassium hydroxide and about 20 to 30% by weight of potassium chloride when an electrolyte permeable barrier is used. It may be a catholyte. The catholyte product may also contain 10 to 45% by weight of sodium hydroxide or 15 to 65% by weight of potassium hydroxide when the ion permeable diaphragm is a cation selective ion permeable membrane inserted between the anode and the cathode.

When an electric current is supplied from the cathode chamber to the anode chamber, an oxidant, such as oxygen, air or oxygen-rich air, is supplied to the cathode chamber so that there is almost no gaseous hydrogen product, chlorine at the anode and alkali at the cathode. It is desirable to produce metal hydroxides. The present invention relates in particular to a preferred coating layer cathode containing the coating particles described herein.

According to a further aspect of the present invention, an anode chamber composed of a material resistant to concentrated chlorinated alkali metal chloride saline, an anode in a cathode chamber, a cathode chamber made of a substance resistant to a concentrated alkali metal hydroxide solution, a cathode device and an anode in a cathode chamber An electrolytic cell is provided that includes an ion permeable diaphragm provided between an anode and a cathode device. The electrolytic cell used in the present invention is characterized by having a cathode chamber including a device for supplying an oxidant to the electrolyte in the cathode chamber and a cathode device composed of individual particles.

In another preferred embodiment of the method of the invention using the above-mentioned particles to produce peroxides, the hydroxide aqueous solution is supplied to the electrolytic cell described above, except that no ion exchange membrane is used. The anolyte feed is typically an aqueous solution containing 15 to 100 g / l sodium hydroxide. The catholyte recovered from the electrolytic cell may be a catholyte containing from about 0.5 to 3% by weight of hydrogen peroxide and 15 to 100 g / l sodium hydroxide.

As described herein, when an electric current is supplied from the cathode chamber to the anode chamber, an oxidant such as oxygen, air or oxygen-containing oxygen is supplied to the cathode chamber, so that there is almost no gaseous hydrogen product. In the form of oxygen and water, and in the cathode, alkali metal hydroxides and peroxides. The present invention relates in particular to a cathode device consisting of coated particles, which is used to carry out the reaction.

According to a further aspect of the present invention, an anode chamber composed of a material resistant to a thick alkali metal hydroxide solution, an anode in a cathode chamber, a cathode chamber made of a material resistant to a concentrated alkali metal hydroxide solution, a cathode device and a cathode in a cathode chamber An electrolytic cell composed of an ion permeable diaphragm provided between an anode and a cathode device is provided. The electrolytic cell used in the present invention is characterized by having a cathode chamber including a device for supplying an oxidant to the electrolyte in the cathode chamber and a cathode device composed of individual porous particles.

Example 1

To prepare a catalytically active coating, 0.7 g of carbon black was mixed with 20 ml of a silver acetic acid solution having a concentration of 10 g of silver acetic acid per liter of solution. Next, one ^{drop of a} surfactant ( ^Triton® X-100, manufactured by Rohm & Haas Co.) is added to increase the wettability of the carbon black. The mixture is then oven dried at about 100 ° C. The mixture is then heated at 350 ° C. for 1 hour under a nitrogen atmosphere to pyrolyze silver acetate. This material is then mixed with 3.5 g of a 1: 10 aqueous emulsion (Teflon ^® 30B, manufactured by EI doupont de Nemours & Co, 10 parts water per part of fluoropolymer). In this way, a slurry was formed, in which -10 to +20 U. S. Add 10g mesh particles. After mixing, the material is dried at about 100 ° C. It is then heated at 350 ° C. for 1 hour under a nitrogen atmosphere. The resulting particles are graphite particles having a carbon-flocarbon-silver coating on the graphite particles surface.

Example 2

The electrolytic cell is assembled as described above. This electrolyzer has an anode and a cathode separated by a porous asbestos diaphragm. The negative electrode is a packed layer of particles prepared in Example 1, and the positive electrode is titanium coated with ruthenium oxide.

A sodium chloride brine solution at a concentration of about 300 g per 1 liter of NaCl is injected into the anode chamber having the anode, and oxygen gas is introduced between the gaps of the particles constituting the cathode. At a voltage of about ² V and a current density of about 1 amp / in ² , a current is passed between the anode and the cathode, causing electrolysis of the brine solution. Chlorine gas is produced at the anode and sodium hydroxide is produced at the cathode.

Claims (22)

An electrode material, characterized in that it is a coated particle having an average diameter of 0.3 mm to 2.5 cm, consisting of a substrate partially or wholly coated with a mixture of a binder and an electrochemically active electrically conductive catalyst. The electrode material of claim 1, wherein the substrate is selected from agglomerates in which the sintered material, the solid material and the small particles are bound. 3. The electrode material of claim 2, wherein the substrate is selected from steel, iron, nickle, platinum, copper silver and graphite. 4. Electrode material according to claim 1, 2 or 3, characterized in that the coating consists of a binder of a hydrophobic polymer material and a catalyst having a surface area of 100 to 1000 cm 2 / g. 5. The electrode material of claim 4, wherein the catalyst is an oxygen reaction catalyst selected from carbon black, activated carbon, platinum and silver. The electrode material of claim 5, wherein the catalyst is carbon black and the surface area of the catalyst is 150 to 500 m 2 / g. 5. An electrode material according to claim 4, wherein the catalyst is a catalyst for decomposition of peroxides selected from silver, platinum and their and carbon black mixtures and compounds. An electrode material according to claim 1, wherein the particles have an average diameter of 0.7 mm to 4 mm. The electrode material according to claim 1, wherein the substrate is a mixture of a solid fluorinated carbon binder and a catalyst selected from silver, carbon black, platinum and activated carbon. Forming a fluid mixture of an electrochemically active electrically conductive catalyst and a binder, solidifying the fluid mixture to bind the catalyst to a substrate, and forming the electrode material into particles having an average diameter of 0.3 mm to 2.5 mm. , To prepare an electrode material. The method of claim 10, wherein the binder is heated to a temperature above the softening point of the binder to form a fluid mixture, and the fluid mixture is cooled to a temperature below the softening point of the binder to bind the catalyst to the substrate. The method of claim 10, wherein the catalyst, binder and substrate are dispersed in the liquid to form a fluid mixture, and the fluid mixture is heated to evaporate the liquid to bind the catalyst to the substrate. The method of claim 10, wherein the binder is dissolved in a solvent to form a fluid mixture, and the fluid mixture is heated to evaporate the solvent to bind the catalyst to the substrate. The method of claim 10, wherein the catalyst is carbon black, the binder is polytetrafluoroethylene, and the weight ratio of carbon black to binder is 4: 1 to 1: 4. The method of claim 10 wherein a surfactant is added to the mixture. The method according to claim 10, wherein the total amount of the catalyst in the mixture is 1 to 35% by weight of the peroxide decomposition catalyst and 65 to 99% by weight of carbon black by adding a second catalyst which is a peroxide decomposition catalyst. . Supplying an aqueous electrolyte solution to the electrolyzer, passing an electric current between the anode and the cathode (where these phases are the electrode material consisting of a substrate partially or wholly covered with an electroconductive mixture of a hydrophobic material and one or more catalysts). The electrode material is composed of a plurality of filler particles having an average diameter of 0.3mm to 2.5cm), recovering the electrolysis product, characterized in that the anode liquid electrolyte chamber having a positive electrode and the negative electrode liquid electrolyte having a negative electrode A method of electrolyzing an aqueous electrolyte solution in an electrolytic cell containing yarns. 18. The method of claim 17, wherein an ion permeable diaphragm is placed between the anode and the cathode. 19. The method according to claim 17 or 18, wherein an oxygen-containing gas is supplied to the cathode. An anolyte electrolyte chamber with a positive electrode, a catholyte electrolyte chamber with a negative electrode, an apparatus for supplying an aqueous electrolyte solution to an electrolyzer, a device for passing current between an anode and a cathode, and an apparatus for recovering electrolysis products from an electrolyzer, wherein At least one of the anode and the cathode consists of an electrode material consisting of a substrate partially or wholly coated with an electroconductive mixture of a hydrophobic material and one or more catalysts, the electrode material having a mean diameter of 0.3 mm to 2.5 cm An electrolytic cell, characterized in that consisting of charged particles. 21. The electrolytic cell of claim 20, wherein the substrate is made of graphite, the catalyst is selected from carbon black, silver and platinum and the hydrophobic binder is pletetrafluoroethylene. 21. The electrolytic cell of claim 20, wherein the catalyst is a mixture of carbon black and a catalyst for decomposition of peroxides.