KR101292059B1 - Membrane-electrode assembly, electrolytic cell employing the same, electrolytic-water sprayer, and method sterilization - Google Patents

Abstract

The present invention, at least one rod-shaped or tubular electrode; A tubular diaphragm disposed around an outer circumference of the electrode; And a linear counter electrode disposed around an outer circumference of the diaphragm, wherein the diaphragm is fixed to the rod-shaped or tubular electrode by the linear counter electrode, thereby forming the diaphragm and the rod. A membrane-electrode assembly is provided which forms an electrode chamber having gas-liquid passages between shaped or tubular electrodes.

Diaphragm, gas-liquid passage, electrode chamber

Description

Membrane-ELECTRODE ASSEMBLY, ELECTROLYTIC CELL EMPLOYING THE SAME, ELECTROLYTIC-WATER SPRAYER, AND METHOD STERILIZATION

The present invention relates to a membrane-electrode assembly for producing electrolytic water for use in sterilization, cleaning, etc., an electrolytic cell employing such an assembly, an electrolytic water sprayer comprising such an electrolytic cell, and a sterilization method using the same.

Disinfectant / Disinfectant Solution:

Chlorine compound fungicides such as sodium hypochlorite, calcium hypochlorite, and sodium dichloroisocyanurate have been widely used as fungicides / disinfectants in a wide range of environments. Among them, hypochlorite including sodium hypochlorite is generally used in view of price and effectiveness. However, there have been many proposals for improvement in the sterilization / disinfection effect required in various fields including the clinical field and the food industry (for example, Japanese Patent Laid-Open No. 2001-253803 and Japanese Patent Laid-Open No. 2001-342496). And Japanese Patent Laid-Open No. 2002-145710).

Typically, such fungicides / disinfectants are prepared by adding each component constituting the composition to water, or by mixing an aqueous solution containing the respective components.

Use electrolyzed water as a substitute:

However, the use of large amounts of chlorine compound fungicides creates a problem. For example, in factories and retail stores where foodstuffs are handled in large quantities, cleaning is done with sodium hypochlorite solutions having concentrations in excess of 100 ppm. However, such cleaning is considered problematic because it not only spoils the flavor of the food but also creates a risk (increasing THM).

In order to mainly eliminate this problem, constant research has been conducted on the utility of electrolyzed water, ie, water produced by electrolysis, in agriculture, food, clinical and other fields. Replacement with electrolytic or ozonized water is mainly in progress in Japan. Using clean energy, electrical energy, hydrogen, oxygen, ozone, hydrogen peroxide, and the like can be synthesized through chemical reaction on the electrode surface while controlling the reaction. In particular, the oxidation reaction at the anode yields efficient oxidizing agents (effective chlorine and peroxides such as ozone) for water treatment, and in some cases generates active species such as OH radicals (Ohms). `` Fundamental Knowledge of Strongly Acidic Electrolytic Water '' published by Shah Corporation.

Attention has been focused on the excellent sterilization / disinfection activity of electrolyzed water, and research is being conducted on clinical activity and the use of water at home. Examples of uses under study include sterilization / disinfection of wounded sites, incision sites, percutaneous openings for static catheters, and the like; Household utensils or articles such as kitchen utensils, baby items, furniture; And household facilities such as toilet facilities and bathtubs. Such electrolyzed water is obtained by means of electrolyzed water (water to be electrolyzed) in which a solute, for example sodium chloride, which is dissolved and generates ions is optionally added together with an acid for pH control.

Type of Electrolyzed Water:

In addition to being used as food additives, electrolytic water can also be used for other applications. In an electrolytic cell containing only water, the following anodic reaction generates oxygen in accordance with equation (1). However, depending on the catalyst and the electrolysis conditions, ozone is calculated according to equation (2), and ozone water including dissolved ozone can be synthesized.

2H ₂ O = O ₂ + 4H ⁺ + 4e (1)

3H ₂ O = O ₃ + 6H ⁺ + 6e (2)

When water contains hydrochloric acid or chloride ions, hydrochloric acid is calculated according to equations (3) and (4). When water contains sulfuric acid, the reaction represented by Formula (5) proceeds to yield persulfuric acid.

_{^{Cl - = Cl 2 + 2e (}} 3)

Cl ₂ + H ₂ O = HCl + HClO (4)

2SO ₄ ^2- = S ₂ O ₈ ^2- + 2e (5)

When carbon ions are present, the reaction represented by formula (6) proceeds to yield percarbonate.

2CO ₃ ^2- = C ₂ O ₆ ^2- + 2e (6)

Through the cathode reaction, according to the formulas (7) and (8), it is possible to synthesize hydrogen water (hydrogeneous water), alkaline ionized water, and the like, in which excess hydrogen is dissolved and contained.

2H ⁺ + 2e = H ₂ (7)

_{2H 2 O + 2e = H 2} + 2OH - (8)

In addition, hydrogen peroxide or the like may be synthesized.

As mentioned above, in addition to the acidic water approved as a food additive, electrolyzed water containing two or more peroxides can be produced by an appropriately selected electrolyte.

Characteristics of Electrolyzed Water (Characteristics of Water And Novel Application Technology, 2004, NTS Inc.):

There are three kinds of electrolyzed water approved as food additives.

a) Alkali electrolytic hypochlorite water (additive name, electrolytic sodium hypochlorite water; 20-200 ppm; pH> 7.5; calculated from 0.2-2% aqueous sodium chloride solution without diaphragm)

b) weakly acidic electrolyzed water (additive name, weakly acidic hypochlorous acid, 10-30ppm, pH = 5-6.5, calculated from 2-6% hydrochloric acid without using a diaphragm)

c) Strong acid electrolyzed water (additive name, strong acid hypochlorous acid, 20-60 ppm, pH <2.7; calculated as anode water from low aqueous sodium chloride solution of 0.2% or less in diaphragm type cells)

Acidic water in this kind of electrolytic water has the following advantages, for example.

(1) Under acidic conditions, acidic water is excellent in terms of stability since THM is unlikely to occur.

(2) It is less likely to develop resistant bacteria and easy to manage on site.

(3) This water can be used for combination treatment with alkaline electrolyzed water.

(4) This water can be used like tap water and does not leave any residual smell on your hands or fingers.

(5) It is enough to use this water just before (the sterilization time is short).

In conventional treatment with sodium hypochlorite solution, it has been allowed to use the compound as a food additive up to 200 ppm concentration. However, this compound undermines the flavor of the food and leaves residual tendency. On the other hand, although the initial investment of the device is required for use, such kind of electrolyzed water is beneficial because it has a high sterilizing effect even at low concentrations.

Characteristics of Ozone Water:

Long-term use of hypochlorite results in bacteria that are resistant to such compounds, and the bactericidal effect thereof is suspected. On the other hand, ozone water has been on the list of food additives and has been approved by the US FDA (2001) for use as a fungicide in food storage / production processes. Ozone water has been widely applied for sterilization of food factories and for sterilization of food itself. In recent years, attention has been focused on the fact that ozone water is equivalent to or better than the sterilizing water used so far in clinical fields such as dermatology, ophthalmology, and dentistry, and reduces the burden on the living body. .

Ozone water has the following advantages, for example.

(1) The bactericidal effect of ozone (OH radicals) is based on oxidative destruction of cell walls, which is thought to not produce resistant bacteria.

(2) Ozone does not leave any residual.

When ozone water is used in combination with an oxidizing agent (e.g. hypochlorite, persulfate, or percarbonate) having a residual feeling as needed, more efficient sterilization treatment is possible.

Conventional process for producing ozone water:

In general, ozone water has been conventionally produced using a discharge type ozone gas generator. Ozone water having a concentration of several ppm can be easily produced by this process and is used in the fields of water purification treatment and food cleaning. However, this apparatus is not suitable for use as a simple ozone water production apparatus having excellent instantaneous reactivity and producing high concentration ozone water for the following reasons.

(1) Ozone water production requires two steps, first producing ozone as a gas and then dissolving the gas in water.

(2) Ozone water has a lower concentration than that produced by the electrolytic process described later, and therefore, it should be produced by dissolving it by high pressure injection into water.

(3) The power for ozone generation is high pressure and high frequency, so size reduction is difficult.

(4) In the ozone water producing apparatus based on discharge, a certain period of time (a few minutes of waiting time) is required for the ozone gas generating ability to stabilize, and thus it is difficult to instantaneously produce ozone water having a predetermined concentration.

Electrolytic Ozone Production Process:

The electrolytic process is inferior to the discharge process in terms of power consumption. However, the characteristic of the electrolytic process is that high concentration ozone gas and ozone water are easily obtained. Thus, electrolytic processes are commonly used in special fields such as, for example, cleaning of electronic components. Since a DC low voltage power source is adopted due to the principle of this process, it is expected that this device is excellent in terms of instantaneous reactivity and stability and is used as a small ozone gas generator or a small ozone water producing device. Depending on the application, the drive mode may be selected from battery drive, power generation drive, and AC-DC conversion drive.

In order to produce ozone gas efficiently, it is essential to select the appropriate catalyst and electrolyte. Known electrode materials include precious metals such as platinum, α-lead dioxide, β-lead dioxide, glassy carbon impregnated with fluorine carbide, diamond and the like. As electrolytes, aqueous solutions containing sulfuric acid, phosphoric acid, fluorinated groups and the like have been used. However, such electrolytes are not widely used because of poor handleability. A water electrolysis cell, which adopts a rigid polymer electrolyte as a diaphragm and uses pure water as a raw material, is generally used because it is easy to manage from such a viewpoint [J. Electrochem. Soc., 132,367 (1985). When lead dioxide, which has been employed as a catalyst, is used, ozone gas having a concentration of 12% or more is obtained.

In a system called a direct synthesis system, the solution located around the electrode flows at a sufficient rate to obtain ozone as ozone water before vaporization (Japanese Patent Laid-Open No. 8-134677). In addition, when raw water other than pure water is supplied to the electrolytic system, the activity of the noble metal electrode catalyst itself is influenced by the nature of the water. It is worth noting that electrolytic performance, such as lifetime and efficiency, changes. Japanese Patent Laid-Open No. 9-268395 discloses that conductive diamond is useful as an electrode for producing functional water (including ozone).

Development of small devices:

In order to facilitate sterilization / disinfection in clinical activities or at home, portable or compact electrolytic water production / discharge apparatus has been proposed (see Patent Documents 1 to 3). Such small devices may be widely used for deodorizing, disinfecting or bleaching of internal or water-related equipment or tableware or clothing for home or business purposes or for disinfection or disinfection of the human body, such as for example hands or fingers.

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2000-79393

[Patent Document 2] Japanese Laid-Open Patent Publication No. 2000-197889

[Patent Document 3] Japanese Patent Application Laid-Open No. 2001-276826

In addition to this: Japanese Patent Laid-Open No. 2004-129954 (apparatus having a device for generating electric power for electrolysis); Japanese Patent Application Laid-Open No. 2004-130263 (a device in which the ratio of the volume and the piston capacity of the cell cylinder portion, the cross section, etc. are of specific values); Japanese Patent Application Laid-Open No. 2004-130264 (apparatus for obtaining electrolyzed water having a pH of 3 to 8.5 using electrolytic raw water containing a pH regulator, a surfactant, a chlorine compound and water); Japanese Laid-Open Patent Publication No. 2004-130265 (electrolyzed water according to Japanese Laid-Open Patent Publication No. 2004-130264 is used in a bubble state); Japanese Patent Application Laid-Open No. 2004-130266 (the direction of applying a voltage to an electrode alternately); Japanese Patent Application Laid-Open No. 2004-148108 (the voltage to be applied to the voltage is variable); Japanese Patent Application Laid-Open No. 2004-148109 (apparatus having electrodes in suction passage); Japanese Patent Application Laid-Open No. 2003-93479 and Japanese Patent Laid-Open No. 2002-346564 (separation type having a cylindrical electrode in the spraying section); And Japanese Laid-Open Patent Publication No. 2001-47048 (gun type having a motor which is prevented from clogging during a period without spraying) is known.

Known techniques for synthesizing ozone water include the following. Japanese Patent Application Laid-Open No. 2000-169989 discloses an assembly consisting of a cylindrical shaft of a solid body, a metal-gauze-like anode (platinum) wound around the shaft, an ion exchange membrane, and a metal gauze cathode A small electrolytic ozone generator having a configuration comprising a, disposed in a water channel, the shaft having a shallow groove. Japanese Patent Laid-Open No. 2001-198574 includes a rigid cylindrical shaft, a porous anode fixed to the shaft, a rigid polymer electrolyte (ion exchange membrane), and a porous cathode, and includes ozone water to be synthesized at the anode and hydrogen to be synthesized at the cathode. Disclosed is a module for piping connection which is capable of releasing hydrogen gas separately. Japanese Laid-Open Patent Publication No. 2002-143851 discloses a water treatment method using a double-pipe structure including a support cylindrical member having a through hole, a cathode wound around the cylindrical member, a membrane, and an anode. In this method, by passing a dilute aqueous solution of sodium chloride through a cylinder functioning as a cathode chamber, it is possible to prevent hard-water components from being deposited from tap water as raw water, and ultraviolet treatment can also be performed simultaneously. Japanese Patent Application Laid-Open No. 2004-60010 and Japanese Patent Application Laid-open No. 2004-60011 can separate an electrolytic cell corresponding to that described in Japanese Patent Application Laid-Open No. 2000-169989, and an electromotive force measuring device disposed in a channel. An ozone water production apparatus capable of measuring the concentration of ozone is disclosed. Japanese Laid-Open Patent Publication No. 2006-346203 discloses the use of conductive diamond as an electrode, and in particular, a rod-shaped conductive diamond electrode, a strip-shaped diaphragm member disposed around the electrode, and a line shape disposed on the diaphragm member. An electrolytic cell comprising a counter electrode of is disclosed. Further, Japanese Laid-Open Patent Publication No. 2007-136356 discloses a cylindrical core member having a groove extending in the cylindrical direction, and a structure including a cathode, a membrane, and an anode wound around the core member in the following order.

Summary of the Invention

Conventional small electrode assemblies and electrolytic cells employing the assemblies have the following problems.

(1) The use of an ion exchange membrane or the like improves the ion conductivity, which is expected to effectively increase the electrolysis reaction, but it was difficult to combine the membrane and the like with the electrode.

(2) The membrane is usually nonporous and is used in combination with a porous electrode to promote the feeling of the electrolyte and the removal of the product. Thus, the shape of the electrode assembly is complicated.

(3) When the assembly is attached to the apparatus, the piping film is often cylindrical, and therefore, preferably, the electrode has a shape suitable for the piping member, for example, a rod shape or a cylindrical shape. It was necessary to adopt a device suitable for the shape.

(4) Although platinum catalysts are superior in their properties of accelerating ozone generation, they are unstable and susceptible to raw water. When tap water is used as it is, in some cases, ozone water having a concentration of several ppm that enables short term sterilization cannot be synthesized.

(5) In calculating ozone water, hydrogen generated at the counter electrode is separated to increase the partial pressure, which inevitably leads to an increase in solution concentration. However, no cell has a structure suitable for it.

If these problems are overcome, the use of electrolyzed water in homes, hospitals, nursing homes, etc. is expected to spread further.

It is an object of the present invention to provide a membrane-electrode assembly that can solve many of these problems and is easily productive and exhibits high performance. Another object of the present invention is to provide an electrolytic cell, an electrolytic water sprayer, and a sterilization method employing the assembly, respectively. The electrolyzed water sprayer of the present invention electrolyzes the original aqueous solution, and the resulting electrolyzed water can be used immediately.

Firstly, the present invention

At least one rod-shaped or tubular electrode;

A tubular diaphragm disposed around the outer periphery of said electrode, preferably an ion exchange membrane; And

A linear counter electrode disposed around the outer circumference of the diaphragm

/ RTI &gt;

The membrane is fixed to the rod-like or tubular electrode by the linear counter electrode, thereby forming an electrode chamber having a gas-liquid passage between the diaphragm and the rod-shaped or tubular electrode. Provide an electrode assembly.

Secondly, the present invention

At least one rod-shaped or tubular electrode;

A tubular diaphragm disposed around an outer circumference of the electrode; And

Porous counter electrode disposed around the outer periphery of the diaphragm

/ RTI &gt;

The membrane is fixed to the rod-shaped or tubular electrode by the porous counter electrode, thereby providing a membrane-electrode assembly for forming an electrode chamber having a gas-liquid passage between the diaphragm and the rod-shaped or tubular electrode. .

Thirdly, the present invention

At least one rod-shaped or tubular electrode having a recess formed therein;

A tubular diaphragm disposed around an outer circumference of the electrode and forming an electrode chamber having a gas-liquid passage therebetween; And

Plate-shaped counter electrode disposed around the outer peripheral portion of the diaphragm

It provides a membrane-electrode assembly comprising a.

According to the present invention, an electrolytic cell and an electrolyzed water sprayer each having a membrane-electrode assembly can be constructed. The electrolyzed water sprayer can be used to calculate the electrolyzed water and to eject the electrolyzed water to the object to be sterilized.

Hereinafter, the present invention will be described in detail.

A tubular diaphragm, such as an ion exchange membrane, is disposed around the outer periphery of a rod-shaped or tubular electrode, typically an anode (hereinafter also referred to as a rod anode), and a linear or porous counter electrode, typically a linear or wire The cathode of the electrode is disposed around the outer periphery of the membrane, the membrane is fixed to the cathode such that the membrane contacts at least a portion of the anode and the membrane contacts at least a portion of the cathode, between the membrane and the anode and preferably a plurality of The membrane-electrode assembly of the present invention is characterized as being fabricated by forming a gold plating chamber having a gas-liquid passage between the anodes.

In the present invention, an anode chamber separated from the cathode chamber by a diaphragm is formed to constitute an appropriate gas-liquid passage. By changing the water supply rate and the current value, the concentration of species in the electrolyzed water produced by electrolysis can be adjusted to the desired value.

In the following description, a rod electrode and a counter electrode are used as the anode and the cathode, respectively. However, in the present invention, the rod electrode and the counter electrode may be used as the cathode and the anode, respectively.

This membrane-electrode assembly has a configuration comprising a rod anode, a sheet-like membrane disposed around the outer periphery of the anode in a manner to form a tube, and a cathode wound thereon at an appropriate pitch. In this configuration, an anode chamber in which the rod anode, the membrane, and the wire cathode can not only partially contact each other, but also the generated liquid and gas can move helically through it, between or between the rod anode and the membrane. It may be formed between a plurality of rod anodes.

A membrane-electrode assembly with an ideal passage is obtained by appropriately selecting the diameter and number of rod anodes, the diameter of the tubular membrane, and the material, thickness and winding pitch of the line cathode. In particular, by spirally winding the wire cathode at a pitch of 1 to 10 mm, an assembly having an appropriate structure is obtained. It is particularly preferable that the anode is made of diamond, because such an assembly can efficiently generate ozone or the like.

This membrane-electrode assembly can be used to construct an electrolytic cell comprising a tube fixed to at least one of the openings of the anode chamber and one or two feed terminals connected to the anode and / or the cathode.

Further, the cathode chamber can be formed between the cathode and the diaphragm by fixing the tube to two openings of the anode chamber formed between the anode and the diaphragm and fixing the generated member to the second tube having at least two openings. One or two feed terminals are connected to the positive electrode and / or the negative electrode. Thus, the electrolytic cell can be configured such that electrolysis is performed while supplying raw water to one of the openings of the anode chamber and also supplying raw water to one of the openings of the cathode chamber as necessary. The diaphragm is deformed to form an anode chamber between the diaphragm and the anode, and the cathode chamber is also formed in a spiral. Because of this, gases and liquids near the cathode in the cathode chamber can flow helically. In such cells, acidic and alkaline water can be synthesized simultaneously in the anode chamber and the cathode chamber, respectively.

When raw water passes through the electrolytic cell and voltage is applied to the cell, the raw water comes into contact with the rod electrode and the counter electrode of the electrolytic cell and is electrolyzed to produce electrolyzed water.

This electrolytic cell is mounted in an electrolyzed water jetting device having a vessel containing raw water and a head. When raw water is absorbed and passed through the tube and voltage is applied to the electrolytic cell, the raw water comes into contact with the positive and negative electrodes of the electrolytic cell and is electrolyzed to yield electrolytic water. This electrolyzed water is atomized through the nozzle of the head which optionally has power assistance, such as, for example, a pump, or discharged to the outside as a liquid state.

Alternatively, the electrolytic cell may be connected directly to the water supply line. Raw water is supplied from the water supply line to the anode chamber or cathode chamber, electrolyzed while being supplied, and then active electrolytic water is produced.

In such electrolytic cells, active species such as ozone are efficiently synthesized at high concentrations to yield electrolyzed water with bactericidal / bleaching ability. The concentration of ozone or other species in the electrolyzed water depends on the amount of raw water flowing in each chamber per unit time. The area of the cross section through which raw water flows can be adjusted by adjusting the diameter and number of rod anodes, the diameter of the tubular membrane, and the winding pitch of the line cathodes. Thus, the electrolyzed water can be generated efficiently.

The method of the present invention and the electrolytic water sprayer of the present invention are intended for deodorization, sterilization, or bleaching, water-related equipment, tableware, clothing, etc. of indoor equipment for home or business purposes, or for sterilization of a human body such as, for example, hands or fingers. And widely used for disinfection. As is clear from the foregoing description, the term "sterilization" in the sterilization method of the present invention means any of actions such as deodorization, bleaching and disinfection in addition to sterilization.

In the present invention, the following highly active electrolytic water can be calculated by adjusting the conditions.

(1) Alkali electrolytic water (alkali water containing dissolved hydrogen gas)

(2) acidic electrolytic water (electrolyzed water containing two or more peroxides calculated by electrolyte selection (in addition to chlorides, sulfates, carbonates, etc. can be used))

(3) high concentration ozone water (this water has no tendency to remain and has a bactericidal activity of 10 times or more of the bactericidal activity of the hypochlorite system, and has a bleaching effect; the ozone half-life is extended by some coexisting substances, Achieve improvement)

(4) New synthetic electrolytic water (a novel bactericidal effect caused by the addition of an organic acid or surfactant for pH adjustment for the purpose of improving sterilization activity, or the addition of alcohols for the purpose of improving sterilization activity or freshness, for example) Has

A rod electrode, a membrane, and a counter electrode are arranged by arranging an ion exchange membrane in the form of a sheet around a periphery of at least one rod electrode in a manner of forming a tube, and by arranging a linear counter electrode or a porous electrode around the at least one rod electrode. Are combined with each other. Because of this, the assembly once created is easy to handle. This assembly can be easily produced.

Gas / liquid passages suitable for use as electrode chambers (or as electrode chambers and counter electrode chambers) can be controlled by adjusting the diameter of the rod electrode, the cross-sectional shape of the electrode, the diameter of the tubular membrane, and the winding pitch in the case of the linear counter electrode. Or by selecting such a diameter of the tube in which such a member is disposed to form the counter electrode chamber and also appropriately determining the number of rod electrodes to be used. By changing the water supply rate and the current value, the concentration of the electrolytically calculated species in the electrolyzed water can be adjusted to the desired value.

The obtained electrolytic water is sprayed or sprayed on the object to be sterilized, where the object can be sterilized by the electrolytically produced species contained at the desired concentration.

The components of the present invention will be described below. However, the present invention should not be considered limited thereto.

Anode and anode material:

Examples of the anode catalyst for oxidation include noble metals such as lead oxide, tin oxide, and platinum, DSA (electrodes mainly composed of noble metal oxides), carbon, and conductive diamond. In view of corrosion resistance, it is preferable to use a noble metal such as platinum or iridium, an oxide of such a noble metal, or conductive diamond as an electrode catalyst. The material used as the electrode base is preferably corrosion resistant in terms of obtaining a long life and preventing contamination of the surface to be treated. It is preferable to use a valve metal such as titanium or niobium or an alloy thereof as the anode base. The anode material may be deposited on the surface of such a base having a shape commonly used so far, such as a pipe or rod. Although the cross section is preferably selected from circles, squares, ellipses, etc. or from hollow cylinders, hollow prisms, and the like, but is not limited thereto. Treating the surface of the rod-shaped or cylindrical anode to give recesses and protrusions, or in the case of hollow materials, forming openings in the electrode surface is effective in improving gas-liquid permeability. In addition, a base obtained by rolling a metal gauze in a tubular form can be used. The height of the recesses and protrusions is preferably 0.1 to 5 mm. It is also possible to use a base having a spiral groove extending in the cylindrical direction.

By using a plurality of anodes instead of forming recesses and protrusions on the surface of the anode, it is possible to easily and reliably form a liquid passage and improve gas-liquid permeability. In particular, when rod-shaped or cylindrical anodes are arranged in a line, adjacent anodes are in close contact with each other and the contact area of the anode and the diaphragm decreases, thus creating a large space between the anodes and between the anode and the diaphragm. Form. Thus, a liquid passage (anode chamber) can be formed without cumbersome work such as surface treatment of the anode.

The plurality of rod-shaped electrodes may be partially replaced by a member composed of a base on which no catalyst is formed. In this case, this member forms a liquid passage and serves to flow a current to the other rod-shaped electrode (s).

The presence of the catalyst is sufficient as part of the anode, and the base may be partially exposed.

Diamond is considered to be a somewhat promising electrode material because its electrical conductivity can be regulated by doping. Diamond electrodes are inert in water decomposition reactions. Diamond electrodes have been reported to produce ozone and hydrogen peroxide in addition to oxygen. When conductive diamond is used, the electrolysis reaction proceeds more easily and its peroxide as a product of electrolysis is produced very efficiently. In addition, in the diamond electrode, in addition to the electrolytically calculated material described above, OH radicals and an electrolyte in oxidized form are produced. Thus, the bactericidal / bleaching effect of OH radicals and electrolytically produced materials in oxidized form can be used synergistically.

When conductive diamond is used, examples of useful bases include Nb, Ta, Zr, Ti, Mo, W, graphite, and various carbides and Si (monocrystalline and polycrystalline). A suitable one can be selected according to the use.

Cathode Materials, Cathode Feeders:

Cathode reaction includes hydrogen evolution as a main reaction. Therefore, an electrode catalyst which is not broken by hydrogen is preferable. Examples of such preferred electrode catalysts include platinum group metals, nickel, stainless steel, titanium, zirconium, gold, silver, carbon, and diamond. As a negative electrode base, it is preferable to use stainless steel, zirconium, carbon, nickel, titanium, etc.

Preferably the shape is in the form of a wire. In addition to being linear, the cathode may be a thinly cut metal gauze or foil. In the case of a linear form, the cathode may be a winding obtained by twisting a plurality of thin filaments. This form is also preferred. In the case of using a line cathode, such a line cathode sometimes functions as a feeder. In the present invention, this feeder is included in the line cathode.

The porous metal gauze cathode may be rolled up in a tubular form and deposited around the outer periphery of an ion exchange membrane or the like. Examples of porous cathodes include, in addition to metal gauze, expanded meshes and perforated metals. In the case of using such a material, it is preferable to form recesses and protrusions on the surface of the anode to form an anode chamber between the ion exchange membrane and the anode. However, the anode chamber may be formed by only deforming such a porous cathode to partially project the diaphragm toward the anode.

The diaphragm in which the catalyst layer was previously formed in the one surface, for example, the ion exchange membrane may be arrange | positioned so that the surface which has a catalyst may face outward. This configuration is preferred because the electrolytic cell can have a uniform current distribution and thus a reduction in cell voltage can be achieved. In order to form the catalyst layer, existing techniques such as electroless plating and PVD can be used. In this case, the metal wire which also functions as a feeder is wound there. Preferred examples of feeder materials include platinum group metals, nickel, iron, copper, silver, gold, stainless steel, titanium, and zirconium.

Diaphragm material:

As the diaphragm, an ion exchange membrane or a neutral membrane can be used. Typically, ion exchange membranes are used.

The diaphragm not only prevents the material produced at the anode or cathode from being consumed at the counter electrode, but also has the function of allowing the electrolysis to proceed quickly even when using a liquid having a low conductivity. Therefore, the use of a diaphragm is preferable in the case of using a raw material having a low conductivity, such as pure water. In the case of using an ion exchange membrane, it may be either a fluorinated resin membrane or a hydrocarbon resin membrane. However, in view of resistance to corrosion by ozone and peroxide, the former film is more preferable. The thickness of the membrane is preferably 0.1 to 1 mm.

In the case where the line cathode is wound around the membrane to form a spiral passage, it is preferable to use a commercial membrane containing the reinforcing fibers and having a high mechanical strength as the membrane.

It is preferable to form a septum in a tubular shape beforehand. This can be easily accomplished by a known tube forming treatment technique using a precursor resin having thermoplasticity. In connection with the diaphragm, it is preferable to include reinforcing fibers. It is also possible to use a method in which the sheet-like film is rolled into a tubular shape and then bonded. In the case of fluorinated resin ion exchange membranes, it is also possible to use a method in which the edge portions of the membranes overlap and are then thermally fused together or fixed to each other by an adhesive. In thermal fusion, the appropriate range and area pressure of the treatment temperature are 200 to 350 ° C and 2 to 20 kg / cm ^2, respectively. The suitable range of treatment time is 1 second to 1 minute. In order to increase the bonding strength and achieve more complete bonding, it is desirable to bond the ion exchange membranes through narrow strips of fluorinated resin membranes that do not contain reinforcing fibers.

It is preferable to form recesses and protrusions on the membrane surface because the gas-liquid permeability can be improved.

Membrane-electrode assembly:

The length and diameter of the rod anode in the membrane-electrode assembly is chosen according to the desired amount. Usually, the length is preferably 10 to 300 mm, and the diameter is preferably 0.5 to 10 mm. The diameter of the diaphragm in the assembly is adjusted to be about 0.1 to 5 mm larger than the diameter of the rod anode (usually cylindrical) disposed in the diaphragm.

The percentage of the opening of the porous cathode is preferably 20 to 80%, and the thickness thereof is preferably 0.1 to 2 mm.

In the case of using a wire cathode (feeder wire), the diameter is preferably in the range of 0.1 to 2 mm.

If the line cathode is thinner than that, the voltage loss cannot be ignored due to the electrical resistance. In addition, such thin cathodes have insufficient physical strength and are prone to breakage during winding operations. If the line cathode is too thick, the movement of the raw material of electrolysis and the product of electrolysis from the anode chamber is prohibited, resulting in an increase in voltage and a decrease in current efficiency. In addition, such thick cathodes are difficult to wind.

When the line cathode or feed line is wound spirally on the outer surface of the anode and the membrane, the line cathode pitch is preferably 0.1 to 10 mm.

When the wire cathode is wound in a spiral, the winding angle depends on the diameter and number of rod electrodes, the width of the diaphragm, and the diaphragm gap.

Even when raw water having a low conductivity is used, the electrodes are in helical contact with at least a portion of the membrane to facilitate electrolysis, and the anode chamber formed by the anode and the membrane smoothly feeds the supplied raw water and generated gaseous components into the anode chamber. In view of the need to have a capacity to make it flow, the aforementioned dimensions are selected / designed.

Electrolytic cell:

At least one of the openings in the anode chamber formed by the anode and the diaphragm in the membrane-electrode assembly was fixed to a tube connected to the raw water channel. This tube has a diameter almost equal to that of the tubular diaphragm. The diaphragm and the tube are fixed to each other with an adhesive, and the feed terminal to the rod anode is connected to the anode of the tube.

In addition, a member obtained by fixing the tube to each of the two anode chamber openings of the assembly may be disposed in a second tube having at least two openings and separated from the member. Thus, the cathode chamber can be newly formed between the second tube and the membrane. The feed terminal to the line cathode is connected to the cathode in the second tube.

Raw water is supplied to one of the openings of the anode chamber, and raw water is also supplied to one of the openings of the cathode chamber, depending on the necessity of performing electrolysis. Electrolyzed water is calculated by supplying an element to the anode chamber opening and performing electrolysis while selectively supplying water to the cathode chamber opening. Therefore, if necessary, alkaline water and acidic water can be simultaneously produced.

The inner diameter of the second tube forming the cathode chamber is adjusted to be about 0.1 to 5 mm larger than the diameter of the membrane of the assembly. If the second tube is thinner than that, mass transfer in the catholyte is prohibited and, in particular, there is a possibility that the deposition of hard-water components from tap water is accelerated. On the other hand, when the second tube is too thick, the catholyte has a reduced flow rate and it becomes impossible to separate and remove the hard water component by the liquid flow rate. This results in an increase in voltage and a decrease in current efficiency. In addition, the amount of water stored in the cell increases, making it impossible to obtain alkaline water immediately.

The material of the second tube is preferably a hydrocarbon resin such as PP, PVC or PE, a fluorinated resin, a metal tube and the like. Since the capacity of the electrolytic cell portion can be adjusted, a tube having heat shrinkability is preferable. The wall thickness of the second pipe is preferably small from the viewpoint of quickly removing heat generated in the electrolytic cell. However, since mechanical strength is also required, the wall thickness is preferably up to 0.05-2 mm.

The water first released from the electrolysis cell contains raw water that has not been sufficiently electrolyzed. In this respect, the amount of water present in the electrolytic cell and the capacity of the other parts of the piping are preferably smaller.

In order to prevent the wires from coming into contact with each other, the two feed wires extending from the electrode are preferably covered with an insulating material. Each feed line from the second tube is preferably inserted into a heat shrinkable cladding tube and the cladding tube is fused to the line, thereby separating the line from the electrolytic water channel of the unit.

In the case of synthesizing ozone water, if the length of the second pipe extending from the electrolytic cell to the device outlet is too small, it is not preferable because raw water in which ozone is not sufficiently dissolved is ejected. The longer the gas-liquid contact time, the more gaseous ozone is dissolved in raw water, and the efficiency of its synthesis can increase. Therefore, it is preferable to adjust the optimal length so as to have a contact time in the range of 0.1 to 10 seconds.

The material of the container for storing the raw water and the material of the piping are selected from those which are not damaged by the raw water. This material may be PE as long as there is no special problem.

With respect to the electrolysis conditions, in terms of the stability and activity of the material to be produced, the temperature and the current density are preferably 5 to 40 ° C. and 0.01 to 1 A / cm ^2, respectively.

Raw Water And Electrolyzed Water Calculated:

Tap water, well water and the like can be used as raw water. In this case, it is preferable to pass water through the cathode chamber to prevent the deposition of Ca and Mg. It is also desirable to make the raw water weakly acidic.

Since such water has a low conductivity, there are cases where it is desirable to increase the conductivity because the resistive loss of the cell voltage is not negligible. In this case, it is preferable to dissolve a salt such as Na ₂ SO ₄ , K ₂ SO ₄ , NaCl, KCl, or Na ₂ CO ₃ as an electrolyte. Such salts often present peroxides upon electrolysis and thus confer a lasting bactericidal effect. The concentration is preferably in the range of 0.01 to 10 g / L. For example, since an electrode such as platinum has a property of improving ozone generating efficiency when chlorine ions are present, it is preferable to prepare raw water in consideration of such characteristics.

When using raw water containing a large amount of metal ions such as tap water, well water, or sea water, there is a possibility that hydroxides or carbonates are deposited on the surface of the cathode to prevent the reaction. In addition, oxides such as silica are deposited on the anode surface. To eliminate this problem, a reverse current is passed at appropriate time intervals (1 minute to 1 hour) where acidification and alkalinization occur at the cathode and anode, respectively. As a result, the reaction for removing the deposits easily proceeds while being accelerated by the gas discharge and the flow of raw water.

The composition and concentration of the electrolyzed water to be calculated can be adjusted according to the purpose. When electrolytic water is used for food processing, it should be produced as alkaline electrolytic hypochlorite water, weakly acidic electrolytic water, or ozone water. However, when electrolytic water is used for sterilization / bleaching, the peroxide may be appropriately selected depending on the material to be treated. In the case of hypochlorous acid, the concentration may be 1 to 100 ppm. Ozone water may have a concentration of 1 to 20 ppm. The concentration of persulfate and percarbonate may be 1 to 100 ppm and 1 to 100 ppm, respectively.

When hypochlorous acid is electrolytically produced, electrolysis of the acidic solution yields a higher amount of hypochlorous acid than hypochlorite, and the use of alkaline aqueous solution yields a higher amount of hypochlorite than hypochlorous acid. Bactericidal activity varies depending on the nature of the solution. In general, acidic solutions often have higher bactericidal activity than alkaline solutions. In particular, in the control of spores and the like, the acidic solution has higher sporicidal activity than the alkaline solution. In contrast, with respect to fungicidal activity, alkaline aqueous solutions are more active than acidic aqueous solutions. Therefore, the nature of the solution must be properly adjusted whether it is acidic or alkaline depending on the material to be treated, thus giving an enhanced bactericidal or fungal removal activity.

When the solution is acidified by adding a strong acid to the solution to excessively increase the acidity, hypochlorous acid is decomposed to produce chlorine gas, and as a result, the oxidizing power causing the bactericidal activity of the hypochlorous acid is reduced. In order to increase the bactericidal activity while maintaining the oxidizing power of hypochlorous acid, it is preferable to make the solution have a pH of 3-7 at 20 ° C. In order to control the solution to have such a pH, it is preferable to use a water-soluble organic weak acid having a low dissociation degree in view of the ease of pH adjustment of the solution. Examples of water soluble organic acids include succinic acid, lactic acid, acetic acid, citric acid, and tartaric acid.

In order to alkalinize a solution, it is preferable to use sodium carbonate, sodium hydrogencarbonate, ammonium carbonate and the like. Such carbonates are oxidized to percarbonate by electrolysis.

In order to further enhance bactericidal activity, a surfactant may be added to the solution. Adding a surfactant to the solution not only improves the solution's ability to wet the material to be treated after electrolysis, but also improves the affinity of the solution for cell membranes of fungi and bacteria. Thus, the bactericidal or mildew removing effect is further improved.

Examples of available surfactants include anionic surfactants such as alkylbenzenesulfonic acid salts and polyoxyethylene alkyl ether sulfates, cationic surfactants such as benzalkonium chlorides, amphoterics such as amine oxides (eg alkyldimethylamine oxides) Nonionic surfactants such as surfactants, polyglycerol fatty acid esters and alkylglycosides. The concentration of the surfactant in the solution is preferably about 0.01 to 10% by weight.

In addition to these components, for example, alcohol may be added to the solution for the purpose of improving bactericidal or mildew removing activity and freshness. Also, if desired, for example, perfumes, colorants, bactericides other than surfactants, thickeners, enzymes, bleaches, chelating reagents, electrolytes other than chlorine compounds, builders, preservatives, and rust preventives. ) May be added. In view of storage stability, it is particularly preferred that the water to be electrolyzed comprises a preservative.

Electrolyzed Water Sprayer (Trigger Spray):

The electrolyzed water sprayer includes a vessel containing raw water and a head connected to the upper opening of the vessel. Although the container may be rigid or flexible, the container is preferably made of a rigid material selected from, for example, various rigid resins, metals, glass, and ceramics. The volume of the container is preferably about 10 to 1,000 mL, more preferably 200 to 500 mL.

The trigger sprayer is fixed to the head where the battery can be housed. The device may be equipped with equipment that does not employ a battery as a power source and generates power for electrolysis by a trigger action. Instead of using a simple primary battery, a rechargeable secondary battery or capacitor may be used. It is also possible to operate a device having an adapter capable of supplying DC power from an AC power source.

The values of voltage and current to be applied are appropriately determined depending on the concentration suitable for deodorizing, sterilizing, or other sterilizing activity suitable for the material to be treated, and the volume of the solution to be electrolyzed. One trigger action causes 0.1–1 cc of ejection and a voltage of about 3–40 V is applied between the electrodes. Equipment for changing the voltage to be applied to the electrode may be disposed in the circuit.

A switch for initiating / terminating the voltage application to the electrode is placed in the trigger sprayer so that the voltage is applied only when the device is in use, i.e. automatically switched on when the trigger is pulled off and off when the trigger is returned. )

The electrolyzed water sprayer may have a device that generates power for electrolysis in the production operation. An example of such a device is a motor that cooperates with a trigger. Such a motor is typically placed in a trigger sprayer.

The electrolyzed water sprayer may have means for indicating that electrolysis is to be performed. Examples of such means include LED lamps that are turned on during voltage application by a trigger action. For example, a function of switching off the LED lamp may be added when a specified current does not flow, for example, for battery exhaust.

The electrolyzed water sprayer is operated by the following structure. The nebulizer is switched on by the trigger action, allowing current to flow through the circuit. As a result, current flows through the electrode. In this operation, the raw water present in the tube is electrolyzed almost instantaneously and sprayed or sprayed out through the nozzle of the head by the piston / cylinder structure. That is, in this nebulizer of the present invention, electrolysis is performed simultaneously with the production operation (for example, trigger operation). The electrolyzed water preferably begins to be calculated by electrolysis within 1 second after the start of the trigger operation.

In addition to the embodiments shown in the figures, there are various embodiments of electrolyzed water sprayers with trigger sprays. In addition, trigger sprays with various structures exist. The trigger spray differs in the liquid passage, the support point of the trigger, and the like depending on the structure thereof. However, any desired trigger spray can be employed for the nebulizer of the present invention.

Next, the electrolytic water sprayer of this invention is demonstrated with reference to embodiment shown to drawing. BRIEF DESCRIPTION OF THE DRAWINGS It is a front view which shows the electrolytic water sprayer as one Embodiment of this invention. FIG. 2 is an enlarged exploded view of the essential part of the nebulizer shown in FIG. 1. FIG. 3 is an oblique view of the electrolytic cell shown in FIGS. 1 and 2.

The electrolyzed water sprayer (trigger spray) 1 shown in FIG. 1 comprises a vessel 3 containing raw water 2 and a head 4 connected to the upper opening of the vessel 3. The raw water 2 may be pure water or may be dissolved therein one or more electrolytes such as, for example, sodium chloride, potassium chloride, and magnesium chloride.

In the container 3, an electrolytic cell 6 composed of an anode, a cathode, and a diaphragm is disposed. As shown in Fig. 2, this electrolytic cell 6 comprises: an anode 7, which is a metal rod electrode on which a catalyst is deposited; A diaphragm 8 which is a tubular ion exchange membrane wound around the anode 7; And a line cathode 9 which is a metal wire wound around the diaphragm 8. The diaphragm 8 is obtained by winding a square sheet so as to be circular when viewed from above and joining two ends along the longitudinal direction.

The diaphragm 8 does not originally have a recess / protrusion. However, by winding the line cathode 9 in the diaphragm 8, the portion of the diaphragm 8 in contact with the line cathode 9 is strongly pushed against the anode 7 and is not in contact with the line cathode 9. A portion of the diaphragm 8 is bent outward to form a spiral anode chamber 10 between the anode 7 and the diaphragm 8.

In addition, the space in the container 3 outside the diaphragm 8 constitutes a cathode chamber.

The tube for the feeder holder 13 was connected to the upper end of the rod anode 7 via a cylindrical connecting tube 12 having a short length. The feed line 14 is held between the inner surface of the connecting pipe 12 and the outer surface of the pipe for the feed line holding portion 13, and the end of the feed line 14 is connected to the upper end of the anode 7.

The upper end of the pipe for the feeder holder 13 fits into the vertical pipeline 15 in the head 4, and the upper end of the vertical pipeline 15 connects to the horizontal pipeline 16 in the head 4. In communication with each other.

At the other end of the horizontal pipeline 16, a spray nozzle 17 is arranged. The support point 19 of the trigger arm 18 is disposed slightly inward of the spray nozzle 17 such that the trigger arm 18 moves around the support point 19. The trigger arm 18 is connected to the piston rod 20 extending inward so that the piston rod 20 moves in the cylinder 21 as the trigger arm 18 moves.

Reference numeral 22 denotes a trigger-associated switch arranged to contact the trigger arm 18, reference numeral 23 denotes a power battery disposed in the head 4, and reference numeral 24 denotes when electrolysis is in progress. Indicates an LED that is only on.

The electrolytic water sprayer 1 having the above-described configuration is held in hand and a force in the inward direction is applied to the trigger arm 18 using the index finger and the middle finger. As a result, the trigger arm 18 moves around the support point 19, the trigger-associated switch 22 is turned on and a voltage is applied to the electrolytic cell 6. At the same time, the piston in the cylinder 21 moves to bring the raw water 2 in the container 3 into contact with the electrolytic cell 6, which is electrolyzed to produce electrolyzed water. The anode 7 in this electrolytic cell 6 has a catalyst, for example, a conductive diamond layer deposited on its surface. Thus, electrolyzed water containing ozone or other active substance dissolved in high concentration is obtained. Since the spiral anode chamber 10 is formed inside the diaphragm 8 of this electrolytic cell 6, an appropriate gas-liquid passage is formed in the anode chamber. Therefore, the concentration in the electrolytic water of the electrolytically calculated species can be adjusted to a desired value by changing the water supply rate and the current value.

The resulting electrolyzed water passes instantaneously through the vertical pipelines 15 and the horizontal pipelines 16 and through the spray nozzle 17 the air introduced through the external air intake opening, not shown, for the material to be sterilized. Sprayed together.

4 is a partial cross-sectional view showing another electrolytic cell according to the present invention. This figure shows an embodiment employing a porous cathode and an anode, which are provided with recesses and protrusions.

The electrolytic cell 32 is comprised from an anode (rod electrode), a cathode (relative electrode), and a diaphragm. The electrolytic cell 32 includes an anode 34 which is a rod electrode made of metal having a spiral groove 33 formed in the outer circumferential portion; A diaphragm 35 formed in a tubular shape and disposed around the outer circumferential portion of the anode 34; And a porous cathode 36 having a shape of a metal gauze, an expanded mesh, or a perforated metal and disposed around the outer circumference of the diaphragm 35.

Unlike the embodiment shown in FIGS. 1-3, in this embodiment there is substantially no deformation of the septum 35 relative to the anode 34 by the porous cathode 36. However, since the anode 34 has a groove 33 formed in the outer circumferential portion, this embodiment includes the anode chamber 37 formed between the anode 34 and a part of the diaphragm 35 corresponding to the groove 33. Has

In this embodiment, a suitable gas-liquid passage is formed in the anode chamber, and the concentration of the species electrolytically calculated in the electrolytic water can be adjusted to a desired value by changing the water supply rate and the current value.

Embodiments in which the anode has recesses and protrusions should not be considered limited to having grooves. Although the above embodiment adopts a rod-shaped or tubular anode having a circular shape when viewed from above, the shape of the anode is not limited thereto. For example, the anode may have a shape as shown by the front views of FIGS. 5 and 6.

The diaphragm 41 of FIG. 5 is a vertically tubular shape obtained by rolling a square sheet and overlapping and joining a part 42 of two ends. The rod anode 43 has a hollow cylindrical shape with protrusions 44 protruding outward from each of the six portions of the base. The tubular diaphragm 41 extends on and around the six protrusions 44. A total of six anode chambers 45 are thus formed between the diaphragm 41 and the anode 43.

Also in the case of FIG. 6, the diaphragm 46 has a vertically tubular form obtained by overlapping and joining a portion 47 of two ends thereof without rolling a rectangular sheet. The tubular anode 48 has a shape obtained from a prismatic base by forming a recess 49 pressed inward at each of the four corners. The tubular diaphragm 46 extends on or around the total eight base portions of the four recesses 49. An anode chamber 50 corresponding to the shape of the recess 49 is formed between the diaphragm 46 and the anode 48.

FIG. 7 is a partial inclination diagram showing still another embodiment of the electrolytic cell of the present invention, and FIG. 8 is a cross-sectional view of the electrolytic cell of FIG. This embodiment relates to the improvement of the embodiment shown in FIGS. 1-3, and the description of a common member is abbreviate | omitted by assigning the same code | symbol.

In the electrolytic cell 6a shown in Figs. 7 and 8, two anode rods made of niobium and covered with a conductive diamond catalyst are surrounded by an ion exchange membrane 8a to form a two-layer film in the form of a tube, A stainless steel wire serving as the cathode 9a is spirally wound on the film to form an anode-membrane-cathode assembly (electrolyte cell).

According to this embodiment as shown in FIG. 8, the anode 7a is rod-shaped, and a relatively large space is formed between two anodes 7a each having a curved surface. In addition, a relatively large space is also formed between the anode 7a and the ion exchange membrane 8a. This space functions as the anode chamber 10a, and electrolyzed water passes through this anode chamber 10a.

According to this embodiment, unlike the embodiment shown in Figures 4 to 6, the treatment of the anode, which is essentially costly and time consuming, is not required. Nevertheless, this embodiment provides an anode chamber having a volume which is the same or somewhat larger than in the embodiment of FIGS. 4 to 6.

Example

Embodiments relating to the production of electrolytic water according to the present invention will be described below. However, the present invention should not be considered as limited to the following examples. The ozone concentration, hypochlorous acid concentration, persulfate concentration, and percarbonate concentration in each example were determined using an ultraviolet spectrophotometer by iodine measurement using potassium iodine.

Example 1

A conductive diamond catalyst (dopant boron concentration 2,500 ppm) was deposited and a rod made of niobium (diameter 2 mm) was placed as a positive electrode on a tubular ion exchange membrane (Nafion 350, manufactured by Dupont; thickness 0.35 mm, diameter 3 mm). Commercially available platinum wire (0.4 mm in diameter) is spirally wound around the diaphragm as a cathode to obtain an anode-membrane-cathode assembly. The winding pitch was 4 mm. Tubes (4 mm in diameter) were joined to the top and bottom of the assembly, and feed lines from a DC power source were connected to each electrode to obtain an electrolytic cell. Pure water was passed through the anode chamber at a rate of 40 cc / min. Currents of 0.5 A and 1 A were allowed to flow separately. As a result, in this operation, cell voltages were 13V and 19V, ozone water concentrations were 8 ppm and 21 ppm, respectively, and ozone generation efficiency was 13% and 12%, respectively. The temperature of the water at the outlet was about 30 ° C.

This electrolytic cell was connected to a PE resin tube attached to the suction part in the trigger type sprayer shown in FIG. 1. The battery was mounted on the head of the trigger type sprayer. In the circuit portion, electrode terminals were connected to a switch having a variable resistor and wiring. The container is filled with 500 cc of pure water.

The trigger was pulled, the circuit was switched on, and current flowed between the battery and the cell. At the same time, pure water was ejected. The amount of pure water ejected was about 0.5 cc and the amount of electricity flowing through this operation was 0.25 C (0.5 s 0.5 A). The terminal voltage of the cell was 13V. This operation was repeated 100 times. As a result, the ozone concentration of the ejected solution reaching about 50 cc was 8 ppm. The trigger operation was repeated 2000 times, and the resultant ozone water concentration was about 8 ppm.

Comparative Example 1

The same material as in Example 1 was used. The strip of the ion exchange membrane was spirally wound on the anode and the platinum line was wound on the diaphragm to obtain an anode-membrane-cathode assembly. At a rate of 40 cc / min, pure water was passed up through the electrolytic cell in which the membrane-electrode assembly was mounted. Currents of 0.5 A and 1 A were allowed to flow separately. As a result, since the diaphragm was arranged in a helical manner, oxygen and ozone generated at the anode were mixed with hydrogen gas generated at the cathode, and this gas was dissolved to yield the electrolyzed water contained therein. In this operation, the cell voltages were 10 V and 13 V, the ozone water concentrations were 5 ppm and 9 ppm, respectively, and the ozone generation efficiency was 8% and 5%, respectively.

Example 2

A portion of the membrane in the assembly of Example 1, which constitutes two openings of the anode chamber, was fixed to a tube with a diameter of 4 mm. The generated member was placed in a second tube having an inner diameter of 5 mm to form a cathode chamber between the second tube and the membrane. The feed terminal to the line cathode was connected to the cathode in the second tube. An aqueous solution of 2 g / L sodium chloride was supplied to the anode chamber at a rate of 40 cc / min, and water was supplied to the cathode chamber in the same manner. A current of 1 A was allowed to flow. As a result, an alkaline water containing hydrogen and a pH of 11 and an acidic water containing hypochlorite ions in an amount of about 40 ppm were simultaneously produced.

Example 3

The same test as in Example 2 was conducted except that tap water was supplied to the anode chamber and the cathode chamber. As a result, the ozone water calculated at 0.5 A had a concentration of 4.5 ppm (current efficiency of 7.3%).

Comparative Example 2

The same test as in Comparative Example 1 was conducted except that tap water was used as a raw material. As a result, ozone water calculated at 0.5 A had a concentration of 1.5 ppm (current efficiency 2.4%).

Example 4

A circular rod made of titanium and with a platinum layer formed thereon (20 g / m ² ) was used as the anode to produce the same assembly as in Example 1. The same test as in Example 3 was conducted using tap water as a raw material. As a result, the cell voltage at 0.5 A was 12 V, and the ozone water had a concentration of 0.5 ppm.

Example 5

A conductive diamond catalyst (dopant boron concentration 1,500 ppm) was deposited and two rods made of niobium (diameter 2 mm) were formed as a positive electrode and surrounded by an ion exchange membrane (Nafion 324, manufactured by Dupont; thickness 0.35 mm, diameter 3 mm). A two-layer film was formed, and stainless steel wire (0.5 mm in diameter) serving as the cathode was spirally wound on the film to obtain the anode-membrane-cathode assembly shown in FIGS. 7 and 8. The winding pitch was 2 mm.

Tubes (4 mm in diameter) were joined to the top and bottom of the assembly, and feed lines from a DC power source were connected to each electrode to obtain an electrolytic cell. Pure water was passed through the anode chamber at a rate of 40 cc / min. Currents of 0.5 A and 1 A were allowed to flow separately. As a result, in this operation, the cell voltages were 13V and 19V, the ozone water concentrations were 15 ppm and 17 ppm, respectively, and the ozone generating efficiency was 13% and 15%, respectively. The temperature of the water at the outlet was about 30 ° C. Leakage from the coronal membranes occurred little.

While the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the invention.

This application is based on Japanese Patent Application Nos. 2007-296769 (filed November 15, 2007) and 2008-266158 (filed October 15, 2008), the contents of which are incorporated herein by reference.

1 is a front view showing an electrolytic water sprayer as one embodiment of the present invention.

FIG. 2 is an enlarged exploded view of the essential part of the nebulizer shown in FIG. 1. FIG.

3 is an inclination of the electrolytic cell shown in FIGS. 1 and 2.

4 is a partial cross-sectional view showing another embodiment of the electrolytic cell of the present invention.

5 is a plan view of another rod anode.

6 is a plan view of a tubular anode.

7 is a partial inclination showing another embodiment of the electrolytic cell of the present invention.

8 is a cross-sectional view of the electrolytic cell of FIG. 7.

Explanation of symbols on the main parts of the drawings

1: electrolyzed water sprayer

2: enemies

3: container

4: head

6, 6a: electrolytic cell

7, 7a: anode

8, 8a: diaphragm

9, 9a: line cathode

10, 10a: anode chamber

15: vertical pipeline

17: spray nozzle

18: Trigger arm

22: trigger interlock switch

32: electrolytic cell

33: Groove

34: anode

35: diaphragm

36: porous cathode

37: anode chamber

41: diaphragm

43: Rod anode

44: protrusion

45: anode chamber

46: diaphragm

48: tubular anode

49: concave

50: anode chamber

Claims (15)

At least one rod-shaped or tubular anode; A tubular diaphragm disposed around the outer circumferential portion of the anode; And A linear cathode disposed around the outer circumference of the diaphragm / RTI &gt; The diaphragm is fixed to the rod-shaped or tubular anode by the linear cathode, thereby forming an anode chamber serving as a gas-liquid passage between the diaphragm and the rod-shaped or tubular anode, The positive electrode chamber serving as the gas-liquid passage is separated from the negative electrode chamber outside of the diaphragm by the diaphragm, and is a spiral electrode having both ends open. The method of claim 1, A membrane-electrode assembly comprising a plurality of rod-shaped or tubular anodes. The method of claim 1, Membrane electrode assembly, characterized in that the linear cathode is wound in a spiral with a pitch of 1 ~ 10mm. delete At least one rod-shaped or tubular anode formed with a recess; A tubular diaphragm disposed around an outer circumference of the anode to form an anode chamber serving as a gas-liquid passage between the anode; And A plate-shaped cathode disposed around the outer peripheral portion of the diaphragm / RTI &gt; The positive electrode chamber serving as the gas-liquid passage is separated from the negative electrode chamber outside of the diaphragm by the diaphragm, and is a spiral electrode having both ends open. The method according to any one of claims 1 to 3 and 5, And the rod-shaped or tubular anode comprises diamond. delete The membrane-electrode assembly according to any one of claims 1 to 3 and 5; A feed line fixing tube fitted into at least one of the openings of the anode chamber of the assembly; And A feeder line fixed between the opening and the feeder line; Electrolytic cell comprising a. The membrane-electrode assembly according to any one of claims 1 to 3 and 5; And A tube disposed around the anode chamber and the cathode, forming a tubular cathode chamber; Electrolytic cell comprising a. 9. The method of claim 8, An electrolytic cell characterized by producing electrolytic water containing ozone water. 10. The method of claim 9, An electrolytic cell characterized by producing electrolytic water containing ozone water. The electrolytic cell of Claim 8; A container containing raw water; And head / RTI &gt; The raw water is electrolyzed by an electrolytic cell, and the electrolyzed water produced thereby is ejected from the head. Generating electrolytic water by the electrolytic water sprayer of claim 12, The generated electrolyzed water is ejected to the object to be sterilized. Sterilization method using electrolytic water. The electrolytic cell of Claim 9; A container containing raw water; And head / RTI &gt; The raw water is electrolyzed by an electrolytic cell, and the electrolyzed water produced thereby is ejected from the head. Electrolyzed water is produced by the electrolyzed water sprayer of claim 14, The generated electrolyzed water is ejected to the object to be sterilized. Sterilization method using electrolytic water.

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