Classifications

• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F1/00—Treatment of water, waste water, or sewage
  • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
  • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
  • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
  • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
  • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
  • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
  • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
  • C25B1/00—Electrolytic production of inorganic compounds or non-metals
  • C25B1/01—Products
  • C25B1/13—Ozone
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F1/00—Treatment of water, waste water, or sewage
  • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
  • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
  • C02F1/46104—Devices therefor; Their operating or servicing
  • C02F1/46109—Electrodes
  • C02F2001/46133—Electrodes characterised by the material
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F1/00—Treatment of water, waste water, or sewage
  • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
  • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
  • C02F1/46104—Devices therefor; Their operating or servicing
  • C02F1/46109—Electrodes
  • C02F2001/46152—Electrodes characterised by the shape or form
  • C02F2001/46157—Perforated or foraminous electrodes
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2201/00—Apparatus for treatment of water, waste water or sewage
  • C02F2201/46—Apparatus for electrochemical processes
  • C02F2201/461—Electrolysis apparatus
  • C02F2201/46105—Details relating to the electrolytic devices
  • C02F2201/46115—Electrolytic cell with membranes or diaphragms
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2201/00—Apparatus for treatment of water, waste water or sewage
  • C02F2201/46—Apparatus for electrochemical processes
  • C02F2201/461—Electrolysis apparatus
  • C02F2201/46105—Details relating to the electrolytic devices
  • C02F2201/4616—Power supply
  • C02F2201/4617—DC only

Definitions

• the present invention relates to an electrode, an ozone generation device, and an ozone generation method, and more particularly, to an ozone in which a cathode and an anode are arranged with a solid polymer film interposed therebetween, and water is electrolyzed to generate ozone.
• the present invention relates to a generator and an ozone generation method, and an electrode that can be favorably applied to the ozone generator and the ozone generation method.
• Ozone is a substance having a very strong acid-riding power, and the sterilizing, decolorizing, and deodorizing actions derived from the acid-riding power are applied in various fields.
• a sterilization method, a decolorization method, and the like using ozone can be said to be a treatment method without fear of secondary pollution since ozone itself is easily decomposed naturally to oxygen.
• the ozone dissolved in water is further improved, and is generally used for sterilization and the like. For these purposes, there is a need for the development of a simpler and more efficient generation method of ozone gas or ozone water.
• an ultraviolet lamp method As a method for generating gaseous ozone, an ultraviolet lamp method, a silent discharge method, and an electrolysis (electrolysis) method are known (for example, see Patent Document 1).
• the UV lamp method is often used to remove a small amount of odor sources, such as indoor deodorization, where the amount of generated ozone is small.
• the silent discharge method is a general method for generating ozone gas. For example, when air is used as a raw material, nitrogen oxides are generated at the same time. In order to prevent this, it is necessary to provide an auxiliary device that concentrates only oxygen in the power air using oxygen gas as a raw material. In addition, mixing of metal impurities into the ozone gas due to consumption of the metal electrode also poses a problem. Further, ozone gas can be obtained by electrolysis of water. According to this electrolysis method, high-purity and high-concentration ozone gas containing a small amount of water can be easily obtained.
• means for dissolving ozone gas obtained by the above means in water or directly generating it by an electrolytic method is known.
• Ozone gas generated by the silent discharge method or the electrolytic method is passed through a gas-liquid dissolving tower and dissolved in water.
• the power to obtain zon water This causes the equipment to become larger and more complicated.
• an electrolytic cell is constructed by sandwiching a solid polymer membrane between a porous or mesh-like anode and a cathode, and according to the electrolytic method of electrolyzing tap water or pure water using this, ozone water is directly It can be generated and the size of the device can be easily reduced.
• a dioxin lead or platinum which has excellent function as a catalyst, is generally used. It has been. These materials are molded into a porous or mesh shape and used as the anode 3, and the solid polymer film 7 is sandwiched together with an appropriate cathode 5, thereby forming an electrolytic cell 1 as shown in FIG. 1, for example.
• ozone gas or ozone water can be obtained (for example, see Patent Documents 1 and 2).
• lead dioxide tends to change state easily and reduce its ability to generate ozone, so it is necessary to keep it positively polarized by applying a voltage to prevent it. For this reason, it is necessary to mount a backup power supply in case of an emergency such as a power failure, which also makes the device large, complex, and expensive.
• Platinum is used as a relatively stable electrode material. It is known that platinum is gradually consumed and eluted in electrolysis where a large voltage is applied. Therefore, regular replacement is required. Platinum is also a rare precious metal, and its high price is a barrier to its introduction.
• a diamond thin film having conductivity has been proposed as an alternative electrode material.
• the main characteristics of this conductive diamond thin film are that it has excellent mechanical strength, is chemically stable, hardly adsorbs molecules, and undergoes oxidative and reductive decomposition of the solvent.
• Non-Patent Document 1 Hidetoshi Sugimitsu, "Basics and Application of Ozone” Korin, February 1996
• Patent document 1 JP-A-1-139785
• Patent Document 2 JP-A-1-312092
• Patent Document 3 Japanese Patent Application Laid-Open No. 9-268395
• the present invention provides an electrode capable of stably performing electrolysis or the like applying a high voltage and a large current without fear of deterioration or peeling, and an ozone generation device using the electrode.
• the purpose was to provide a method for generating ozone.
• the electrode of the present invention made to achieve the above object is characterized in that it is a self-conducting conductive diamond plate having a porous or net-like structure.
• the electrode of the present invention configured as described above is configured by a self-dimensional conductive diamond plate. Therefore, even when electrolysis or the like in which a high voltage and a large current are applied is performed, the excellent characteristics of the conductive diamond, in which there is no fear of peeling or the like, can be stably maintained. Further, since the electrode of the present invention has a porous or reticulated structure, even if the electrode is in close contact with the entire surface of a solid polymer membrane (V, a so-called ion exchange membrane), etc. It can be performed.
• V solid polymer membrane
• the conductive diamond plate can be manufactured by various methods.
• the conductive diamond plate is manufactured by a microwave plasma CVD method, the following additional effects can be obtained. Occurs. That is, the conductive diamond plate manufactured by the microwave plasma CVD method has good crystallinity, and has excellent mechanical strength and mechanical stability. Therefore, in this case, the durability of the electrode is further improved.
• a self-stereoscopic conductive diamond plate is perforated with a laser or discharge container to obtain a porous or reticulated structure.
• the production becomes easy and the production cost can be reduced.
• it is easy to configure the shape and arrangement of the holes and the like as designed, and it is possible to suppress variations in electrode characteristics and improve the yield.
• the thickness of the conductive diamond plate is 0.2 to 1.0 mm, the following further effects are produced.
• the inner wall surface of the perforated hole generates an oxygen generation reaction due to the oxidative decomposition reaction of water.
• the thickness of the conductive diamond plate be 1. Omm or less (more preferably, 0.8 mm or less).
• the thickness of the conductive diamond plate is desirably 0.2 mm or more (more desirably, 0.4 mm or more). Therefore, as described above, if the thickness of the conductive diamond plate is set to 0.2 to 1.0 mm (more preferably, 0.4 to 0.8 mm), the ozone generation efficiency and mechanical strength may be impaired. And the manufacturing cost of the electrode can be reduced.
• the diameter of the perforated hole is 0.5 to 3. Omm, the following further effects are produced.
• the ease with which the air bubbles escape is closely related to the diameter of the pores. If the diameter is less than 0.5 mm, the air bubbles are extremely difficult to escape.
• the pore diameter is too large, for example, not less than 3. Omm, the three-phase interface per unit area is reduced, and the field where the reactions (1) and (2) occur is relatively reduced. .
• the diameter of the hole is 0.5 to 3.0 Omm (more preferably, 1.0 to 2.0 Omm) .In this case, it is possible to generate ozone extremely efficiently. Become.
• a force that is considered that a plurality of holes may be drilled.
• the interval between the outer peripheries of the holes is 0.2 to 1.5 mm, the following additional effect is obtained. Occurs. From the viewpoint of increasing the three-phase interface, it is desirable that the number of holes is large, but if the distance between the outer peripheries of the holes is too small, for example, less than 0.2 mm, it is sufficient for the conductive diamond plate. What The strength cannot be obtained. For this reason, it is desirable that the above-mentioned spacing be 0.2 to 1.5 mm (more preferably, 0.4 to 0.8 mm) .In this case, it is necessary to efficiently secure the mechanical strength of the anode while ensuring sufficient efficiency. Ozone can be generated.
• the inner wall of the perforated hole may have a taper.
• the following additional effects are obtained. Occurs.
• the inner wall of the hole has a taper like this, if the conductive diamond plate is arranged so that the hole expands outwardly from the solid polymer film, the bubbles can be more easily removed. Therefore, in this case, there is an effect that the bubbles can be more easily removed and the ozone generation efficiency can be increased.
• the ozone generating apparatus of the present invention is an ozone generating apparatus comprising a cathode and an anode disposed with a solid polymer film interposed therebetween, and electrolyzing water to generate ozone.
• the anode any one of the above-mentioned electrodes is used, and a three-phase interface where the anode, the solid polymer film, and water are in contact with each other can be formed.
• the ozone generating apparatus of the present invention can stably generate ozone even when a high voltage and a large current are applied to the electrode, and can easily generate high-purity ozone. As described above, maintenance is also reduced due to the excellent durability of the anode as described above. In addition, since the substance constituting the anode does not elute, high-purity ozone water can be directly obtained by continuously supplying pure water.
• the anode is configured to be smaller than the solid polymer film, and a three-phase interface where the anode, the solid polymer film, and water come into contact with each other is provided on the outer periphery of the anode.
• the following effects can be obtained. That is, in this case, since the three-phase interface is also formed around the anode, the field where the reactions (1) and (2) occur is widened, and ozone can be generated more efficiently.
• the ozone generation device of the present invention is an ozone generation device comprising a cathode and an anode disposed with a solid polymer film interposed therebetween, and electrolyzing water to generate ozone.
• a column-shaped self-conducting conductive diamond having a plurality of columns arranged in parallel on the surface of the solid polymer film is used, and the anode, the solid polymer film, and water are in contact with each other. It may be characterized by being constituted so that a phase interface can be formed.
• the ozone generation device of the present invention is an ozone generation device comprising a cathode and an anode disposed with a solid polymer film interposed therebetween, and electrolyzing water to generate ozone.
• a three-phase conductive diamond having a plurality of pieces and being arranged on the surface of the solid polymer film is used as a three-phase contact between the anode, the solid polymer film, and water. It may be characterized in that it is configured to form an interface. In this case, too, by using a plurality of fragmentary self-stereoscopic conductive diamonds arranged on the surface of the solid polymer film as the anode, the anode, the solid polymer film, and water are brought into contact.
• the number of interfacial three-phase interfaces can be increased favorably. Therefore, it is possible to generate ozone very efficiently by securing a large area where the reactions (1) and (2) occur.
• excellent features such as stability of the conductive diamond are exhibited in the same manner as in the above inventions.
• the production cost can be reduced favorably, for example, by using the waste material of the conductive diamond when other devices are manufactured.
• the ozone generation method of the present invention is an ozone generation method in which a cathode and an anode are arranged with a solid polymer film interposed therebetween, and water is electrolyzed to generate ozone.
• the electrode according to any one of the above, wherein a three-phase interface is formed in which the anode, the solid polymer membrane, and water are in contact with each other.
• ozone can be stably generated even when a high voltage and a large current are applied to the electrode, and high-purity ozone can be easily generated.
• the durability of the anode is excellent as described above, the frequency of replacing the electrode is reduced.
• the substance constituting the anode does not elute, high-purity ozone water can be directly obtained by continuously supplying pure water.
• the anode is configured to be smaller than the solid polymer film, and a three-phase interface in which the anode, the solid polymer film, and water are in contact with the outer periphery of the anode.
• the following additional effects are produced. That is, in this case, since the three-phase interface is also formed around the anode, the field where the reactions (1) and (2) occur is widened, and ozone can be generated more efficiently.
• the ozone generation method of the present invention is an ozone generation method in which a cathode and an anode are arranged with a solid polymer film interposed therebetween, and water is electrolyzed to generate ozone.
• a column-shaped self-stereoscopic conductive diamond arranged in parallel on the surface of the solid polymer film, the anode, the solid polymer film, and water are combined.
• the number of contacting three-phase interfaces can be increased satisfactorily. Therefore, it is possible to secure a large amount of space where the reactions (1) and (2) occur, and to generate ozone very efficiently.
• excellent features such as stability of the conductive diamond are exhibited in the same manner as in the above inventions.
• the ozone generation method of the present invention is an ozone generation method in which a cathode and an anode are arranged with a solid polymer film interposed therebetween, and water is electrolyzed to generate ozone.
• a three-phase interface where the anode, the solid polymer film, and water are in contact with each other is formed by using a plurality of pieces of self-stereoscopic conductive diamond arranged in pieces on the surface of the solid polymer film. It may be characterized by the following. In this case, too, by using a plurality of fragmentary self-stereoscopic conductive diamonds arranged on the surface of the solid polymer film as the anode, the anode, the solid polymer film, and water are brought into contact.
• the matching three-phase interface can be increased favorably. Therefore, a large amount of space where the reactions (1) and (2) occur can be ensured, and ozone can be generated extremely efficiently.
• excellent features such as stability of the conductive diamond are exhibited in the same manner as in the above inventions.
• the manufacturing cost of the device required for implementing the present invention can be reduced satisfactorily, such as by using the waste material of the conductive diamond when other devices are created. be able to.
• FIG. 1 is a schematic diagram showing a configuration of an electrolysis cell according to a conventional example and the present embodiment.
• FIG. 2 is a schematic diagram illustrating a configuration of an anode according to the present embodiment.
• FIG. 3 is an explanatory diagram showing that the reaction at the anode occurs near a three-phase interface.
• FIG. 4 is an explanatory view showing growth of bubbles in the holes of the anode.
• FIG. 5 is a schematic diagram illustrating an example in which a hole in the anode is tapered.
• FIG. 6 is a schematic diagram showing a modified example in which the shape of the hole of the anode is changed.
• FIG. 7 is a schematic diagram showing an example in which the periphery of the anode is separated from the outer peripheral portion of the anode chamber.
• FIG. 8 is a schematic diagram showing a modification in which columnar diamond is used as an anode.
• FIG. 9 is a schematic diagram illustrating a modification using fragmentary diamonds as the anode.
• FIG. 10 is a schematic diagram showing an arrangement of holes in an anode on which an experiment was performed.
• the electrolysis cell 1 as the ozone generation device of the present embodiment has the same configuration as the above-described conventional electrolysis cell 1 except for the configuration of the anode 3 described later. That is, as shown in FIG. 1, an anode 3 and a cathode 5 are disposed with a solid polymer membrane 7 (trade name “Nuff Ion”: manufactured by DuPont) interposed therebetween, and the anode 3 and the cathode 5 are solid polymer The film 7 is fixed in close contact with the surfaces facing each other.
• a solid polymer membrane 7 trade name “Nuff Ion”: manufactured by DuPont
• An anode chamber 13 is formed on the surface of the anode 3, and a cathode chamber 15 is formed on the surface of the cathode 5, and the anode chamber 13 and the cathode chamber 15 have supply ports 13a, 15a and outlets 13b, 15b, respectively.
• the anode 3 is provided with a hole 3a having a diameter of 1 mm in a self-dimensional conductive diamond plate formed into a rectangular plate having a thickness of 0.8 mm by a microwave plasma CVD method.
• the holes were drilled so that the center-to-center distance was 2 mm (that is, the distance between the outer peripheries of the holes 3a was 1 mm).
• the hole 3a was formed by a laser cutter.
• a net-shaped platinum electrode was used as the cathode 5.
• the electrolytic cell 1 of the present embodiment even if a high voltage and a large current are applied between the anode 3 and the cathode 5, the conductive diamond on the anode 3 peels off. Ozone can be generated stably without any problem, and high-purity ozone can be easily generated. In addition, since the anode 3 has excellent durability as described above, maintenance of the device is reduced. Further, since the substance constituting the anode 3 does not elute, high-purity ozone water can be obtained.
• the cathode 5 may be formed of a self-dimensional conductive diamond plate having a porous structure.
• the conductive diamond plate constituting the anode 3 may be manufactured by a method other than the microwave plasma CVD method.
• the hole 3a may be formed in a slit shape having another shape, or a large hole 3a may be formed so that the anode 3 has a mesh shape.
• the holes 3a may be formed by a discharge nozzle or may be made porous in the process of manufacturing the conductive diamond plate.
• the thickness of the anode 3 is 0.2 to 1. Omm (more preferably 0.4 to 0.8 mm) for the following reason. It is desirable that That is, when a DC current is applied between the anode 3 and the cathode 5 of the electrolytic cell 1, an oxygen generation reaction due to an oxidative decomposition reaction of water occurs on the inner wall surface of the hole 3a.
• the reactions (1) and (2) involve three phases of the solid polymer membrane 7 in the hole 3a, the inner wall surface of the hole 3a, and the electrolyte (water) in the anode chamber 13. It occurs most efficiently at the bordering interface. This is because when a reaction occurs in this part, the moving distance of the hydrogen ion is the shortest. In addition, it takes time and cost for film formation to produce a thick conductive diamond plate, and it is not preferable to use a conductive diamond plate that is thicker than necessary as the anode 3. Therefore, the thickness of the anode 3 is desirably 1. Omm or less (more preferably, 0.8 mm or less).
• the thickness of the anode 3 be 1.Omm or less (more preferably 0.8mm or less).
• the thickness of the anode 3 be 0.2 mm or more (more preferably, 0.4 mm or more).
• the ease with which the bubble B escapes is also closely related to the diameter of the hole 3a. If the diameter is less than 0.5 mm, the bubble B becomes extremely difficult to escape. On the other hand, if the diameter of the hole 3a is as large as, for example, 3.Omm or more, the three-phase interface per unit area decreases, and the field where the reactions (1) and (2) occur is relatively reduced. would. For this reason, it is desirable that the diameter (diameter) of the hole 3a is 0.5 to 3.0 mm (more preferably, 1.0 to 2.0 mm). In this case, ozone is generated extremely efficiently. It becomes possible.
• the distance between the outer circumferences of the holes 3a and the holes 3a is 0.2 to 1.5 mm. From the viewpoint of increasing the three-phase interface, it is desirable that the number of the holes 3a is large.However, if the interval between the outer peripheries of the holes 3a and the holes 3a is too small, for example, less than 0.2 mm, sufficient space for the anode 3 is obtained. The strength cannot be obtained. For this reason, in the case where it is desired that the interval is set to 0.2 to 1.5 mm (more preferably, 0.4 to 0.8 mm), the ozone is efficiently removed while sufficiently securing the mechanical strength of the anode 3. It can be generated.
• the inner wall surface of the hole 53a is tapered as in the anode 53 shown in FIG. It is also effective to arrange so that it spreads out (hereinafter referred to as a mortar-type arrangement, and vice versa).
• the periphery of the hole 63a may be formed in a wavy shape, as shown in FIG. It is also effective to form the hole 73a in a star shape, as in the anode 73 shown partially enlarged.
• the anode 3 is configured to be smaller than the solid polymer film 7, and the periphery of the anode 3 is moved from the outer peripheral portion 13 c of the anode chamber 13. It is also effective to form a three-phase interface around the anode 3 by separating. That is, as shown in FIG. 7B, the solid polymer film 7 and the anode 3 disposed inside the outer peripheral portion 13c are usually the same size, or the periphery of the anode 3 is a sealing material. Force that is substantially the same as that shown in Fig. 7 (B) and forms a three-phase interface around the anode 3 as shown in Fig. 7 (A), thereby improving ozone generation efficiency. Can be improved.
• anodes 83 made of columnar (here, quadrangular prismatic) self-supporting conductive diamonds are parallel to the surface of the solid polymer film 7.
• a large number of anodes 93 made of a fragmentary (here, cubic) self-supporting conductive diamond may be arranged on the surface of the solid polymer film 7 as shown in FIG. . Also in these cases, the ozone generation efficiency can be improved by increasing the three-phase interface.
• a diamond electrode having the following parameters was created by drilling holes by laser processing in a rectangular self-contained diamond plate having a thickness of 0.8 mm, 15 mm x 50 mm and synthesized by microwave plasma CVD.
• the arrangement of the holes for example, four types of shapes shown in (A), (B), (C), and (D) of FIG. 10 were adopted.
• the solid polymer film 7 (trade name “Nafio A: The anode 3 and the cathode 5 were arranged on both sides of “DuPont”.
• the cathode 5 was made of reticulated white gold.
• the amount of ozone generated per unit time was as follows. Water was supplied to the anode chamber 13 at a flow rate of 3.2 LZ, and DC electrolysis was performed at 10 A.
• ozone can be generated extremely efficiently, and the ozone generation efficiency can be further improved by increasing the three-phase interface or forming a mortar-shaped arrangement of holes. It was verified that.
• the present invention it is possible to provide an electrode capable of performing stable electrolysis such as application of a high voltage and a large current without fear of deterioration or peeling.
• the present invention can provide an ozone generation device and an ozone generation method that utilize ozone, and can efficiently generate ozone for sterilization.

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• 2005
  • 2005-03-31 JP JP2005104334A patent/JP4220978B2/ja not_active Expired - Lifetime
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