WO2012124206A1 - 還元水の作製方法および還元水作製装置 - Google Patents
還元水の作製方法および還元水作製装置 Download PDFInfo
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- WO2012124206A1 WO2012124206A1 PCT/JP2011/075040 JP2011075040W WO2012124206A1 WO 2012124206 A1 WO2012124206 A1 WO 2012124206A1 JP 2011075040 W JP2011075040 W JP 2011075040W WO 2012124206 A1 WO2012124206 A1 WO 2012124206A1
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- water
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
- A23L2/52—Adding ingredients
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- 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
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
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- 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
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
- A23L2/52—Adding ingredients
- A23L2/54—Mixing with gases
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
- A61K8/965—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution of inanimate origin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/04—Processes using organic exchangers
- B01J39/05—Processes using organic exchangers in the strongly acidic form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/04—Processes using organic exchangers
- B01J39/07—Processes using organic exchangers in the weakly acidic form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/04—Processes using organic exchangers
- B01J41/05—Processes using organic exchangers in the strongly basic form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/04—Processes using organic exchangers
- B01J41/07—Processes using organic exchangers in the weakly basic form
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/08—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents with metals
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- 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
- C02F1/4618—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water
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- 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
- C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
- C02F1/4678—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction of metals
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/10—General cosmetic use
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
- A61K2800/805—Corresponding aspects not provided for by any of codes A61K2800/81 - A61K2800/95
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- 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
- C02F1/4618—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water
- C02F2001/4619—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water only cathodic or alkaline water, e.g. for reducing
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Definitions
- the present invention provides a method for producing reduced water that uses metal magnesium to generate hydrogen in water, an apparatus for producing reduced water, and the like.
- Hydrogen-rich water has an antioxidant effect and protects cells (Non-patent Document 1). In fact, animal experiments and human experiments have demonstrated that they have anti-allergic, anti-inflammatory, and anti-oxidant effects, and are effective in various diseases.
- Non-patent document 2 arteriosclerosis (Non-patent document 2), Alzheimer (non-patent document 3), improvement of memory (non-patent document 4), ll-type diabetes (non-patent document 5), Parkinson's disease (non-patent document 6), liver disorder (Non-patent document 7), Myocardial infarction (Non-patent document 8), Allergy (Non-patent document 9), and the effect of metabolic syndrome (Non-patent document 10) have been reported on experiments using animals and humans.
- Vitamin C which is a typical reducing agent, is hydrophilic or hydrophobic, but cannot always reach the brain and cells. Compared to this, hydrogen is an ideal reducing agent that easily reaches the entire body beyond the hydrophobic cell membrane and the brain barrier (Non-Patent Document 1).
- Hydrogen-rich water is provided by various methods, and a typical example is electrolysis (Patent Document 1).
- Patent Document 1 When an aqueous solution is separated by an ion exchange membrane and a voltage is applied using an electrode, anions are oxidized at the anode and cations are reduced at the cathode.
- Various ions are dissolved in tap water. Which ions are oxidized and reduced depends on the redox potential (reduction potential) of the dissolved ions and the concentration of the ions.
- hydrogen is generated mainly at the cathode, the solution becomes alkaline, and is used as hydrogen-rich water or alkali-reduced water.
- This method requires a device with a built-in electrolyzer, and has a problem that the price of the device is high because a noble metal such as platinum is used as an electrode.
- hydrogen gas is blown into water.
- Hydrogen can be dissolved up to a saturation concentration of 1.6 ppm, but after the hydrogen-rich water is put in a container at the factory, it is stored, put on the market, and sold until it is sold to consumers.
- Patent Document 2 there is a problem that equipment for injecting hydrogen and bottling into the container is necessary, and the cost for the equipment is high.
- Patent Document 3 As a method for producing hydrogen-rich water that is chemically suitable as a beverage, there is a method in which metal magnesium is immersed in water to generate hydrogen, and a stick-like or jug structure is used.
- Patent Document 3 In these methods, hydrogen is generated while metallic magnesium is immersed in water. Compared to the electrolysis method, no special equipment is required, so the price is low.
- the reaction of generating hydrogen due to saturation of magnesium ions in the aqueous solution to which metallic magnesium is added does not occur, and the problem that magnesium hydroxide is deposited on the surface of the metallic magnesium and gradually deteriorates so that hydrogen is not generated. There is.
- the surface of the metallic magnesium must be chemically polished by changing water or periodically using cereal vinegar or the like. Furthermore, there is a problem that hydroxide ions accumulate as hydrogen is generated, and the pH of the hydrogen-rich water exceeds 10 and is not suitable for drinking.
- the method of chemically producing reduced water (hydrogen-rich water) using magnesium metal is cheaper, safer, and less expensive than the electrolysis method. Few. However, there is a problem that the reaction to generate hydrogen does not occur due to the saturation of magnesium ions in the aqueous solution to which metallic magnesium is added, and the problem that the surface of metal magnesium is deteriorated and the reaction to generate hydrogen does not occur despite the presence of magnesium. For this reason, the production efficiency of reduced water (hydrogen-rich water) is disadvantageous.
- the present invention provides a method for improving the efficiency of the hydrogen generation reaction and suppressing the decrease in performance due to deterioration of the metal surface.
- the present invention is a method for producing reduced water (hydrogen-rich water) in which hydrogen is generated using metal magnesium while using a porous solid phase having an ion exchange action, for example, in water.
- the reduction is characterized in that, for example, an anode is installed in a layer obtained by mixing and precipitating a solid phase having an ion exchange action with magnesium metal in water, and applying electricity to a cathode provided in a supernatant of water, for example.
- This is a method for producing water (hydrogen-rich water).
- the present invention is characterized in that, for example, the functional group of the solid phase which is an ion exchange resin is a sulfonic acid group or a carboxylic acid group.
- the present invention functional groups such as sulfonic acid groups and carboxylic acid groups in the solid phase are preferably neutralized with an alkali to form a salt.
- the invention of the present application is characterized in that the anode used for promoting the reaction by applying electricity is made of a material containing carbon. More specifically, the present invention provides the following method for producing reduced water (hydrogen-rich water), reduced water (hydrogen-rich water) production apparatus, and the like.
- ⁇ 1> A method for producing reduced water, characterized in that a porous solid phase is used in a method for generating hydrogen in water using metallic magnesium.
- ⁇ 2> The method for producing reduced water according to ⁇ 1>, wherein the solid phase has an ion exchange action.
- ⁇ 3> The method for producing reduced water according to ⁇ 1> or ⁇ 2> above, wherein the solid phase has an acidic functional group.
- ⁇ 4> The method for producing reduced water according to any one of ⁇ 1> to ⁇ 3>, wherein the solid phase has a sulfonic acid group.
- ⁇ 5> The method for producing reduced water according to any one of ⁇ 1> to ⁇ 3>, wherein the solid phase has a carboxylic acid group.
- ⁇ 6> The method for producing reduced water according to any one of ⁇ 1> to ⁇ 5>, wherein the solid phase is a resin.
- the solid phase is an ion exchange resin.
- ⁇ 8> The method for producing reduced water according to any one of ⁇ 1> to ⁇ 7>, wherein the solid phase removes hydroxide generated on the surface of the metallic magnesium.
- ⁇ 9> The method for producing reduced water according to any one of ⁇ 1> to ⁇ 8> above, wherein metal magnesium is oxidized to generate hydrogen at the cathode.
- ⁇ 10> The method for producing reduced water according to ⁇ 9>, wherein the anode is formed of a material containing carbon.
- ⁇ 12> A food or cosmetic to which reduced water produced by the method according to any one of ⁇ 1> to ⁇ 10> above is added in a liquid, solid, powder, or paste form.
- ⁇ 13> A reduced water producing apparatus that generates hydrogen in water using metallic magnesium, wherein a porous solid phase is used.
- a reduced water preparation apparatus that includes an electrode, oxidizes metallic magnesium, generates hydrogen at the cathode, and produces reduced water, and further includes a solid phase that removes hydroxide generated on the surface of the metallic magnesium.
- An apparatus for producing reduced water characterized by ⁇ 15> The reduced water production apparatus according to ⁇ 13> or ⁇ 14>, further including an anode formed of a material containing carbon.
- the reduced water preparation apparatus according to any one of ⁇ 13> to ⁇ 15>, further including a covering member that covers a surface of the anode.
- the reduced water production apparatus according to any one of the above ⁇ 13> to ⁇ 16>, having first and second redox systems each including an anode and a cathode.
- a device for producing reduced water that generates hydrogen in water using an electrode the device comprising an anode formed of a material containing carbon.
- a reduced water production apparatus that generates hydrogen in water using metallic magnesium the apparatus comprising an anode formed of a material containing carbon.
- the saturation amount of magnesium ions in water is increased, hydrogen generation efficiency and reduced water (hydrogen-rich water) are increased.
- the increase in redox potential due to a decrease in the hydrogen content in the reduced water accompanying a decrease in hydrogen generation due to deterioration of the metal magnesium surface can be moderated, and the sustainability of the reaction can be maintained well.
- a solid phase having an ion exchange action can be easily separated from reduced water (hydrogen-rich water) with metallic magnesium by a filter, so that potable water can be obtained.
- elution of magnesium can be achieved by, for example, bringing the anode into contact with a precipitated layer obtained by mixing a solid phase having ion exchange action in water and metallic magnesium, and applying electricity to the cathode provided in the supernatant of the added water. Encourage the formation of magnesium hydroxide on the metal magnesium surface. Also, by using a material containing carbon as the anode, the hydroxide ions that are inevitably generated along with the generation of hydrogen are converted into carbon dioxide, thereby greatly reducing the magnesium hydroxide deposited on the metal magnesium, thereby The elution efficiency of metallic magnesium can be maintained satisfactorily for a long time.
- Anode In the method for producing reduced water (hydrogen-rich water) and the device for producing reduced water (hydrogen-rich water) of the present invention, hydrogen is generated in water using magnesium metal.
- the oxidation-reduction reaction in water is not particularly limited, but a metal such as magnesium is preferably oxidized at the anode and hydrogen is generated at the cathode.
- the size and shape of the material to be used are not particularly limited, but a granular shape or flake shape of preferably 0.1 mm to 50 mm, more preferably 1 mm to 5 mm is desirable.
- the anode used in this oxidation-reduction reaction is not particularly limited in the type of material used or the structure of the apparatus, but preferably, metals such as stainless steel, copper, aluminum, iron, gold, platinum, silver, titanium, , Formed of a material containing carbon.
- An anode formed of a material containing carbon is particularly excellent in that it can convert a hydroxide ion generated with generation of hydrogen into a carbonate ion and prevent an extreme increase in pH value in the aqueous system. .
- a carbon rod, a carbon-containing resin, a carbon-containing solid phase such as resin-permeated carbon, or the like can be used.
- the weight of the material used as the anode is not particularly limited, it preferably has a weight of 0.1 g to 1 kg, more preferably 1 g to 50 g.
- the shape of the material used as the anode is not particularly limited, but is preferably a rod, more preferably a cylinder. 2.
- Solid Phase A porous solid phase is used in the method for producing reduced water (hydrogen-rich water) and the apparatus for producing reduced water (hydrogen-rich water) of the present invention. It is preferable that the solid phase removes hydroxide generated on the surface of magnesium metal, that is, magnesium hydroxide and the like.
- the solid phase By using such a solid phase, in particular, by using the solid phase in contact with the anode, it is possible to prevent magnesium hydroxide or the like having low solubility in water from covering the surface of the metal magnesium.
- magnesium ions can be dissolved in water.
- the solid phase is preferably ionically bonded with dissolved magnesium ions. This increases the solubility of magnesium in water.
- the reaction for generating hydrogen is continued for a long time in a good state. 2.
- the material of the solid phase and the type of functional group contained in the solid phase are not particularly limited. For example, when an ion exchange resin is added to water together with magnesium metal, an effect of increasing dissolved hydrogen is recognized.
- a cation exchange resin is used.
- the functional group of the cation exchange resin is not particularly limited as long as it has a negative charge in water, but preferably a sulfonic acid group or a carboxylic acid group can be used. More preferably, a sulfonic acid group can be used. Although it is not particularly limited, it is desirable to use, for example, a cation exchange resin in which a salt of an acidic functional group is formed because hydrogen is temporarily generated excessively due to a reaction between the functional group acid and metal magnesium. .
- a neutralization method for forming a salt of an acidic functional group is not particularly limited, and for example, sodium hydroxide is used to form a salt.
- a porous ion exchange resin in particular, a cation exchange resin having an acidic functional group such as a sulfonic acid group or a carboxylic acid group is preferably used as the solid phase.
- a cation exchange resin having an acidic functional group such as a sulfonic acid group or a carboxylic acid group
- a “mesoporous” resin having a hole of an intermediate size can be used. Even a non-porous solid phase can be used.
- the total exchange capacity of the solid phase is not particularly limited, but preferably 0.1 eq (equivalent) / LR (volume of resin after swelling (L)) or more, more preferably 1 0.0 eq (equivalent) / LR (volume of the resin after swelling (L)) or more.
- the amount of the resin to be added as a solid phase is not particularly limited, but is preferably 0.2 ml / g to 500 ml / g, more preferably 2 ml / g to 10 ml / g in terms of volume of the swollen resin, per 1 g of magnesium metal. .
- the solid phase can also be used by mixing with metallic magnesium.
- the mixing ratio (weight ratio) of the solid phase (dry weight), which is a cation exchange resin, and metal magnesium is preferably 1:10 to 25: 1, more preferably 1: 1. ⁇ 5: 1.
- the type and shape of the material are not particularly limited.
- a cathode preferably a metal such as stainless steel, copper, aluminum, iron, gold, platinum, silver, titanium, or a carbon-containing solid phase such as a carbon rod, a carbon-containing resin, or a resin-impregnated carbon, more preferably stainless steel is used. it can.
- Covering member As described above, when a material containing carbon is used for the anode and hydroxide ions are converted to carbon dioxide at the anode, carbon powder may be generated and the water may be contaminated. In order to prevent this, it is preferable to cover the surface of the anode with a covering member that blocks the passage of carbon powder.
- the covering member is not particularly limited, but is preferably a film, paper, cloth, membrane, more preferably a porous film filter such as a resinous membrane filter, glass fiber filter, cellophane, filter paper, etc. By surrounding the anode containing carbon to prevent water contamination. In addition, it is preferable that the covering member allows water, hydroxide ions, carbon dioxide, and carbonate ions to pass therethrough.
- the reduced water (hydrogen-rich water) production apparatus preferably has a plurality of redox systems each including an electrode.
- the electrode the above-described anode and cathode can be used.
- a case that separates the anode and the solid phase from the outside may be provided.
- This case is formed of a nonconductor such as plastic. It is preferable to form a hole in the case and close the hole with a sheet-like member that allows water to pass selectively.
- a sheet-like member for example, Preferably cloth, a filter paper, a film
- the current and voltage applied to each system (circuit) can be adjusted separately, and the dissolved hydrogen concentration in the reduced water (hydrogen-rich water) Fine adjustment of pH becomes possible.
- the shape of the redox system is, for example, a cylindrical shape, but is not limited to this.
- the type of water used in the oxidation-reduction reaction is not particularly limited, but preferably tap water, well water, river water, lake water, seawater, mineral water, distilled water, reverse osmosis water, and more preferably tap water Water, mineral water, etc. can be used.
- the amount of water to be added is not particularly limited, but is preferably, for example, 0.1 ml / g to 1 L / g, more preferably 4 ml / g to 20 ml / g, per 1 g of metal magnesium.
- the pH of the reaction solution is not particularly limited but is preferably pH 3 to pH 14, more preferably pH 7 to pH 12.
- the redox potential after the reaction proceeds is not particularly limited, but is ⁇ 800 mV to 500 mV, preferably ⁇ 300 mV to ⁇ 10 mV.
- the amount of dissolved hydrogen after the progress of the reaction is not particularly limited, but is 0.001 to 1.6 ppm by weight, preferably 0.1 to 1.2 ppm by weight.
- water containing 0.005 ppm by weight or more of hydrogen is defined as hydrogen-rich water. However, this does not exclude from the present invention a method and an apparatus for producing reduced water containing less than 0.005 ppm by weight of hydrogen.
- the type of water for the oxidation-reduction reaction is not particularly limited, but if necessary, a buffer, an oxidizing agent, a reducing agent, an acid, an alkali, a salt, a sugar, an adsorbent, and the like can be mixed and used.
- the filtration method for removing metallic magnesium and solid phase from the water after the reaction is not particularly limited, but a filter such as a nonwoven fabric can be used.
- a filter such as a nonwoven fabric
- the type of current is not particularly limited, but direct current is preferably used.
- Reduced Water Reduced water (hydrogen-rich water) produced by the above production method is used, for example, filled in a spray device and sprayed. Further, the reducing water (hydrogen-rich water) remains in a liquid state, or is processed into a solid, powder, or paste and added to food or cosmetics.
- FIG. 1 The conceptual diagram of the reduced water (hydrogen rich water) preparation apparatus of this invention is shown as FIG.
- the present invention is not limited by this conceptual diagram, but water 2 and a mixture 3 of solid phase and metal magnesium having an ion exchange action are added to beaker 1. Then, the anode 4 is brought into contact with the mixture 3 of solid phase and metal magnesium having an ion exchange action which has been precipitated and formed into a layer, and the cathode 5 is not brought into contact with the mixture 3 of solid phase and metal magnesium having an ion exchange action. Install in water.
- a current is passed through the apparatus using a DC power source 6.
- the voltage to apply is not specifically limited, Preferably it is 0.1V to 1000V, More preferably, 3V to 100V is used.
- the current to be passed is not particularly limited, but preferably 0.1 mA to 1000 A, more preferably 5 mA to 400 mA.
- the form of the produced reduced water (hydrogen-rich water) can be used directly or as a spray.
- the reaction vessel is not particularly limited, but sticks, cups, tanks, water servers, replacement cassettes, and the like can be used.
- the produced water can be directly drinkable, or can be used as food or cosmetics in the form of liquid, solid, powder, paste or the like.
- the “ion” refers to a charged atom or atomic group as an ion. It exists in substances having ion binding properties such as plasma of ionosphere, aqueous solution of electrolyte, and ionic crystal.
- the “ion exchange” is a phenomenon in which an ion species is exchanged by taking in an ion contained in a contacting electrolyte solution, which is exhibited by a certain substance, and releasing another ion of its own instead. It means ability.
- the “resin” is a non-volatile solid or semi-solid substance secreted from the bark. Or it is a substance that has been synthesized by the development of organic chemistry and has properties similar to natural resins.
- the “ion exchange resin” is a kind of synthetic resin and has a structure that ionizes as an ionic group in a part of the molecular structure. It exhibits an ion exchange action with ions in a solvent such as water, but its behavior follows its selectivity for ions. Depending on the nature of the ionic group, it is roughly classified into a cation exchange resin and an anion exchange resin, and it can be divided into strong acid / weak acid, strong base / weak base by its dissociation property.
- the above-mentioned “functional group” is a group of atomic groups focused on chemical attributes and chemical reactivity of a substance, and shows specific physical properties and chemical reactivity, respectively. A group of atoms that gives chemical properties to a compound.
- the “total exchange capacity” is the total amount of ions that can be held by a resin having a certain amount of functional groups.
- the “equivalent” is a concept representing a quantitative proportional relationship in a chemical reaction. One of the typical ones is a molar equivalent representing the ratio of the amounts of substances. Eq is used as the unit.
- neutralization refers to mixing an acid and a base to counteract both properties to form water and a salt.
- the “swelling” is to swell the ion exchange resin by adding water or the like and sufficiently sucking it. Performed before using ion exchange resin.
- the “oxidation reduction” is a reaction in which electrons are transferred between atoms, ions, or compounds in a process in which a product is generated from a reactant in a chemical reaction.
- the “porous” means a state having a large number of small holes (pores) inside a substance possessed by a substance such as an adsorbent typified by activated carbon that plays a role in taking up and adsorbing molecules.
- the “microporosity” generally means a state having a large number of small holes (pores) of less than 2 nm inside a substance.
- the “macroporosity” generally means a state having a large number of small holes (pores) larger than 50 nm inside the substance.
- the “mesoporosity” generally means a state having a large number of small holes (pores) larger than 2 nm and smaller than 50 nm inside the substance.
- the “redox potential” is a potential (correctly an electrode potential) generated when electrons are exchanged in a certain redox reaction system. It is also a scale that quantitatively evaluates the ease with which electrons are emitted or received.
- the unit is bolts.
- the “buffering agent” refers to a solution having a buffering action. Usually, when simply referring to a buffer solution, it refers to a solution having a buffering effect on the hydrogen ion concentration.
- nonwoven fabric refers to a fabric made by bonding or intertwining fibers by heat, mechanical or chemical action without weaving a twisted fiber like normal cloth. Point to.
- the “reverse osmosis water” is a kind of filtration membrane, and refers to water that has passed through water and has a property of not permeating impurities other than water such as ions and salts.
- the “carbon-containing resin” is obtained by kneading and molding carbon powder into a resin. It has features such as conductivity and excellent strength.
- the “resin-impregnated carbon” is a resin infiltrated from a solid surface such as a carbon rod. It has features such as conductivity and excellent strength.
- a “gel” is a material in which a polymer network encloses a liquid. Physical gels that are weakly tied together by high molecular weight are jelly and agar are typical. Chemical gels are the chemical bonds of polymers, including water-absorbing materials and contact lenses. “Polymer” is a compound formed by polymerizing a plurality of unit structures (monomers) (bonded to form a chain or network). For this reason, it is generally a high molecular organic compound. “Copolymer” refers to a polymer comprising two or more types of unit structures (monomers), in particular, as a copolymer.
- the “support” is a substance that serves as a basis for fixing a substance exhibiting adsorption or catalytic activity.
- the carrier itself is desirably chemically stable and does not hinder the intended operation.
- “Hydrogen-rich water” is water containing a lot of hydrogen molecules (hydrogen gas). Since hydrogen molecules do not dissolve in water and become hydrogen ions, hydrogen molecules do not directly affect pH.
- “Electrolysis” is a method of electrochemically inducing a redox reaction by applying a voltage to a compound to chemically decompose the compound. It is also called electrolysis for short.
- the “electrolytic diaphragm” is a porous partition wall disposed between the two electrodes in order to prevent the reaction products of both electrodes from mixing and causing side reactions by electrolysis.
- 200CT NA is a strongly acidic ion exchange resin having an MR structure of a styrene / divinylbenzene copolymer as a carrier, and sulfonic acid is bonded as a functional group.
- IR120B NA registered trademark
- 200CT NA and IR120B NA are each neutralized as a salt with sodium hydroxide at the time of use.
- metals other than magnesium, such as iron and zinc, can be used for hydrogen generation, metal magnesium is particularly suitable from the viewpoints of reactivity, hydrogen generation efficiency, and safety.
- Example 2 In the same manner as in Example 1, the relationship between the amount of the resin and the oxidation-reduction potential was examined using cation exchange resin Amberlite 200CT NA (registered trademark) in which sulfonic acid was bonded as a functional group to magnesium metal and a carrier. It was. After each ion exchange resin was swollen and washed with tap water, 10, 20 or 30 ml was placed in a 100 ml beaker, 5 g of metal magnesium was added, and the final volume was adjusted to 100 ml with tap water. From the next day after the start of the reaction, the water was changed about once every hour about 5 times every day. Also, the oxidation-reduction potential was measured 30 minutes to 1 hour after the first water exchange every morning.
- Amberlite 200CT NA registered trademark
- the sample containing 30 ml of the ion exchange resin had a significantly lower redox potential than the other samples and showed strong reducibility.
- the sample containing 10 ml of the ion exchange resin had a significantly higher oxidation-reduction potential than the other products, and showed a weak reduction property.
- Example 2 In the same manner as in Example 1, experiments were conducted using metallic magnesium, a cation exchange resin Amberlite 200CT NA (registered trademark) in which a sulfonic acid was bonded as a functional group to a carrier. 20 ml of this cation exchange resin was placed in a 100 ml beaker, 5 g of metal magnesium was added, and the final volume was adjusted to 100 ml with tap water. As a comparative control, a sample to which only metallic magnesium was added was prepared. From the next day after the start of the reaction, water was exchanged about once every hour, approximately every hour. The measurement was carried out on the first day of reaction, after 13 days and after 69 days.
- Amberlite 200CT NA registered trademark
- the measurement is performed with a sample containing only metallic magnesium after a specified number of days and a sample containing a cation exchange resin having metallic magnesium and sulfonic acid as functional groups.
- the supernatant of the beaker is discarded, and 100 ml of tap water. Was added and mixed, the supernatant was discarded, and tap water was newly added and finally started as 100 ml.
- the redox potential between 10 and 180 minutes was measured. The results are shown in FIG.
- the oxidation-reduction potential decreased to about ⁇ 140 mV in the sample containing only metal magnesium, but decreased to ⁇ 210 mV when the ion exchange resin having a sulfonic acid group was added.
- the oxidation-reduction potential decreased to about ⁇ 200 mV in the sample containing only magnesium metal, but the cation exchange resin having a sulfonic acid group decreased to ⁇ 260 mV.
- both the sample containing only magnesium metal and the ion exchange resin having a sulfonic acid group similarly decreased to about ⁇ 70 mV. From the first day of the reaction, the effect of improving the hydrogen generation efficiency by the cation exchange resin having a sulfonic acid as a functional group was observed to be sustained, but the effect almost disappeared after 69 days.
- Example 2 In the same manner as in Example 1, the relationship between the amount of the resin and the oxidation-reduction potential was examined using cation exchange resin Amberlite 200CT NA (registered trademark) in which sulfonic acid was bonded as a functional group to metallic magnesium and the carrier. It was. 10 ml, 20 ml or 30 ml of a new cation exchange resin was placed in a 100 ml beaker, 5 g of metal magnesium was added, and the final volume was adjusted to 100 ml with tap water. As a comparative control, a sample to which only metallic magnesium was added was prepared. The redox potential was measured from 10 minutes to 180 minutes. The results are shown in FIG.
- Amberlite 200CT NA registered trademark
- 200CT NA (registered trademark) has sulfonic acid as a functional group on the carrier
- IRC76 (registered trademark) has carboxylic acid as a functional group on the carrier
- IRA400J Cl (registered trademark) has a quaternary ammonium base as a functional group on the carrier.
- IRA67 (registered trademark) has a tertiary amine as a functional group attached to the carrier.
- 200 CT NA has a styrene / divinylbenzene copolymer as a carrier
- IRC76 registered trademark
- IRA400J Cl registered trademark
- IRA67 registered trademark
- IRA67 has an acrylic / divinylbenzene copolymer as a carrier.
- 200 CT NA registered trademark
- IRA400JCl registered trademark
- IRC76 (Registered Trademark) and IRA67 (Registered Trademark) take 20 ml of swollen resin in a 100 ml beaker, add 100 ml of tap water, add sodium hydroxide and hydrochloric acid to 1N each, and overnight. The sum operation was performed. These samples were thoroughly washed with tap water, the pH was adjusted from neutral to weak alkali with hydrochloric acid or sodium hydroxide, and finally 5 g of metal magnesium and tap water were added to finally make the experiment 100 ml.
- the measurement of the ion exchange resin having a carboxylic acid as a functional group is performed by measuring the reaction start date and a sample after 33 days from the start of the reaction, and the ion exchange resin having a quaternary ammonium base as a functional group after the reaction start date and 27 days after the start of the reaction.
- the sample was an ion exchange resin having a tertiary amine as a functional group, and the oxidation-reduction potential was measured for 10 minutes to 180 minutes using the reaction start date and those after 20 days. The results are shown in FIGS.
- an oxidation-reduction potential equivalent to that of an ion exchange resin having a sulfonic acid as a functional group is obtained.
- the redox potential was the same as that of metal magnesium alone.
- the ion exchange resin having a carboxylic acid as a functional group showed a lower oxidation-reduction potential than the ion exchange resin having a sulfonic acid group as a functional group on the reaction start date.
- An intermediate redox potential between an ion exchange resin having an acid group as a functional group and magnesium metal alone was obtained.
- a high reducing action was observed.
- the cathode is fixed to 2 cm ⁇ ⁇ 5 cm and 0.3 mm thick stainless steel (Kuyo Metal Works, sus430), and the anode is 2 cm x 5 cm and 0.3 mm thick stainless steel (Kuhou Metals Co., Ltd. sus430) , Copper (Kyuho Metal Works Co., Ltd.), aluminum (Kuhou Metal Works Co., Ltd.), and a carbon rod (Sea Task Co., Ltd.) having a diameter of 9.5 mm and a length of 10 cm were used for comparative experiments.
- the concentration of produced hydrogen was the lowest, 0.190 ppm, but in the experiment using the carbon rod as the anode, it was 0.440 ppm, and in the case of aluminum, the concentration was 0.40 ppm. It was the highest at 570 ppm.
- the lowest pH was 5.79 in the experiment using the carbon rod as the anode, and the highest pH was 10.07 in the experiment using copper as the anode.
- water stains after electrolysis strong water coloring, white floating matters, and white precipitates were observed in experiments using copper, aluminum, and stainless steel as anodes. Further, when the current was fixed at 60 mA and energized for 1 hour and the dissolved hydrogen concentration and pH were measured, similar results were obtained.
- Example 2 the same metallic magnesium used in Example 1 was added to a 100 ml beaker to the experimental apparatus, and 100 ml of tap water was added.
- the cathode was fixed to stainless steel, and comparative experiments were conducted using stainless steel, copper, aluminum, and carbon rods as the anode.
- a schematic diagram of this experiment is shown in FIG. 10 g of metal magnesium 3 was added to the beaker 1 and tap water 2 was added to make 100 ml.
- the anode 4 is brought into contact with the precipitated metal magnesium 3 and the cathode 5 is placed in water so as not to contact the metal magnesium 3.
- a current was passed through the apparatus using a DC power source 6.
- the voltage was fixed at 24V, which is frequently used in home appliances. After energization for 1 hour, the dissolved hydrogen concentration and pH were measured. The results are shown in FIG.
- the dissolved hydrogen concentration was measured using a dissolved hydrogen meter (UP Corporation, model number ENH-1000). The pH was measured using a pH meter. The carbon dioxide concentration was measured using a dissolved carbon dioxide detection kit (Tetra Japan Co., Ltd. Tetratest (registered trademark)). The results are shown in FIG.
- the dissolved hydrogen concentration was 0.190 ppm in the experiment using stainless steel as the anode, and 0.446 ppm in the experiment using the carbon rod as the anode, and the dissolved hydrogen concentration was higher in the experiment using the carbon rod.
- the dissolution of carbon dioxide in water was as low as 8 g / ml and the pH was as high as 7.58.
- dissolution of carbon dioxide of 40 mg / ml or more was observed in water, and the pH was greatly reduced to 5.79.
- a carbon rod having a diameter of 9.5 mm and a length of 10 cm was used as the anode, and stainless steel having a thickness of 2 cm ⁇ 5 cm and a thickness of 0.3 mm was used as the cathode.
- the experiment was carried out using 10 ml of the same metallic magnesium as used in Example 1 and 20 ml of Amberlite 200CT NA (registered trademark) which is an ion exchange resin having a sulfonic acid group as a functional group.
- a schematic diagram is shown as FIG. A mixture 3 of ion exchange resin and metal magnesium was added to a beaker 1, and tap water 2 was added to make 100 ml.
- the anode 4 was brought into contact with the mixture 3 of the ion exchange resin and metal magnesium which had been precipitated to form a layer, and the cathode 5 was placed in water so as not to contact the mixture 3 of ion exchange resin and metal magnesium.
- a direct current was passed through the apparatus using a direct current power source 6.
- the voltage was fixed at 24V which is frequently used in home appliances.
- the dissolved hydrogen concentration and pH were measured.
- the dissolved hydrogen concentration was measured using a dissolved hydrogen meter (UP Corporation, model number ENH-1000).
- the pH was measured using a pH meter.
- a similar experiment was performed using a material in which only 10 g of metal magnesium was added without adding an ion exchange resin. The results are shown in FIG.
- the dissolved hydrogen concentration after 1 hour was high when the ion exchange resin was added regardless of the addition or non-addition of metallic magnesium.
- Example 1 100 ml of tap water was added to a 100 ml beaker.
- the cathode stainless steel having a thickness of 2 cm x 5 cm and a thickness of 0.3 mm was used, and as the anode, a carbon rod having a diameter of 9.5 mm and a length of 10 cm was used.
- the electrolysis was carried out by applying a direct current using a power source. The voltage was fixed at 24V which is frequently used in home appliances. After energization for 1 hour, the dissolved hydrogen concentration and pH were measured. Similarly, the same magnesium metal used in Example 1 was then added to the experimental apparatus in a 100 ml beaker.
- the cathode was stainless steel, and the anode was a carbon rod.
- FIG. 10 An outline of this experiment is shown in FIG. 10 g of metal magnesium 3 was added to the beaker 1 and tap water 2 was added to make 100 ml. The anode 4 was brought into contact with the precipitated metal magnesium 3 and the cathode 5 was placed in water so as not to contact the metal magnesium 3. A DC current of 24 V was flowed through the apparatus using a DC power source 6. After energization for 1 hour, the dissolved hydrogen concentration and pH were measured. Furthermore, after allowing a natural chemical reaction for 1 hour without passing an electric current with the above apparatus, the dissolved hydrogen concentration and pH were measured. The dissolved hydrogen concentration was measured using a dissolved hydrogen meter (UP Corporation, model number ENH-1000). The pH was measured using a pH meter. The measurement results are shown in FIG.
- the apparatus When electricity was passed through the apparatus without adding metallic magnesium, the apparatus contained no metallic magnesium, but the dissolved hydrogen concentration was 0.468 ppm and the pH was 6.78 after 1 hour of reaction. When metallic magnesium was added and no electricity was passed through the apparatus, the dissolved hydrogen concentration was 0.775 ppm and the pH was 10.53 after 1 hour of reaction. Furthermore, when electricity is passed through the apparatus after adding metallic magnesium, the dissolved hydrogen concentration is 0.715 ppm and the pH is 9.67 after 1 hour of reaction, and reduced water (hydrogen-rich water) with a pH of 10 or less suitable for drinking. was gotten. When electricity was passed through the apparatus to which metallic magnesium was added, no significant difference was found in the dissolved hydrogen concentration compared to the case where electricity was not passed, but a decrease in pH was observed. As the reaction of magnesium metal progresses, its chemical hydrogen generation capacity decreases over the long term. However, when electricity is passed through the electrode of this device, the dissolved hydrogen concentration due to hydrogen generated by electrolysis is This reaction is considered to be maintained separately.
- the films used were ultra high molecular weight polyethylene porous film, Sunmap (registered trademark) (Nitto Denko Corporation), microporous thin film Yumicron (registered trademark) electric field diaphragm (Yuasa Membrane Co., Ltd. MF-90B) and cellophane (Rengo Co., Ltd.). )It was used. The voltage was fixed at 24V which is frequently used in home appliances. Similarly, the same magnesium metal used in Example 1 was then added to the experimental apparatus in a 100 ml beaker. A schematic diagram of this experiment is shown in FIG. 10 g of metal magnesium 3 was added to the beaker 1 and tap water 2 was added to make 100 ml.
- the anode 4 is brought into contact with the precipitated metal magnesium 3 and the cathode 5 is placed in water so as not to contact the metal magnesium 3.
- a current was passed through the apparatus using a DC power source 6.
- the dissolved hydrogen concentration and pH were measured.
- the dissolved hydrogen concentration was measured using a dissolved hydrogen meter (UP Corporation, model number ENH-1000).
- the pH was measured using a pH meter. The results are shown in FIGS.
- the dissolved hydrogen concentration after 1 hour was 0.478 ppm, but cellophane and a microporous thin film Yumicron (registered trademark) electric field diaphragm were used. In this case, it was 0.52 to 0.53 ppm.
- the pH was 6.0 when nothing was wound on the carbon rod, and about 6.5 when cellophane and a microporous thin film Yumicron (registered trademark) electric field diaphragm were used.
- the voltage was fixed at 24 V, and electricity was applied for 1 hour, and the absorbance (wavelength 600 nm) of the solution was measured.
- the absorbance was measured using an ultraviolet-visible spectrophotometer (Shimadzu Corporation UV-160A). It is known that the concentration of fine particles can be known by measuring the absorbance at this wavelength. The results are shown in FIG.
- FIG. 18 is a diagram showing the outline of the apparatus, and FIG. 18A shows the internal structure of the reduced water production apparatus, and as will be described later, this includes two carbon rods serving as anodes, two stainless steel cathodes, and the like. .
- the internal structure of FIG. 18A is wrapped in an internal plastic case, and the internal structure and the case internal structure of the internal plastic case have the appearance shown in FIG. 18B.
- This case internal structure is further wrapped in an external plastic case, and the entire apparatus including the external plastic case has an appearance as shown in FIG. 18C.
- FIG. 19 shows the internal structure (FIG. 18A) relating to hydrogen generation of this apparatus in detail.
- the carbon rod 4 is installed in a plastic case 13 having a hole 7. All the holes 7 are closed by a nylon mesh so that water can pass through but the contents are not leaked to the outside. Further, a stainless steel 5 having a hole 8 on the outer periphery is installed.
- the first carbon rod 4 is an anode, and constitutes a first redox system 10 (first circuit) together with the cathode stainless steel 5.
- the second carbon rod 14 is installed in a second plastic case 16 having a hole 17. All the holes 17 are closed with a nylon mesh so that water can pass through but the contents do not leak out.
- the second carbon rod 14 is an anode, and constitutes a second redox system 20 (second circuit) together with the cathode stainless steel 15.
- first redox system 10 13.1 g of metallic magnesium, 6.6 g of ion exchange resin, and 10.85 g of activated carbon are packed around the first carbon rod 4 installed in the center.
- second redox system 20 that exists next to the first redox system 10 (first circuit) constitutes a second circuit.
- the voltage was fixed at 24 V and only 50 mA was applied to the first oxidation-reduction system 10 (first circuit), and then the dissolved hydrogen concentration and pH were measured. Furthermore, after filling the inside of the cassette with tap water, the voltage was fixed at 24 V and 200 mA was applied only to the second oxidation-reduction system 20 (second circuit), and then the dissolved hydrogen concentration and pH were measured. The dissolved hydrogen concentration was measured using a dissolved hydrogen meter (UP Corporation, model number ENH-1000). The pH was measured using a pH meter. The measurement results are shown in FIG.
- Holes 7 and 17 provided in the first plastic case 13 constituting the first redox system 10 and the second plastic case 16 constituting the second redox system are closed with a nylon mesh. Water can go in and out, but internal materials cannot go out. As a result, carbon dioxide generated from the carbon rod dissolves in water to become carbonic acid and quickly diffuses into the cassette, so that the solubility of carbon dioxide in the cassette can be increased.
- the reduced water (hydrogen-rich water) production apparatus of the present invention may be used by being incorporated in a container such as a stick, a cup, a tank, a water server, or a replacement cassette, or an apparatus.
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Abstract
Description
<2> 固相が、イオン交換作用を有する、上記<1>に記載の還元水の作製方法。
<3> 固相が酸性の官能基を有する、上記<1>または<2>に記載の還元水の作製方法。
<4> 固相がスルホン酸基を有する、上記<1>~<3>の何れかに記載の還元水の作製方法。
<5> 固相がカルボン酸基を有する、上記<1>~<3>の何れかに記載の還元水の作製方法。
<6> 固相が樹脂である、上記<1>~<5>の何れかに記載の還元水の作製方法。
<7> 固相がイオン交換樹脂である、上記<1>~<6>の何れかに記載の還元水の作製方法。
<8> 固相が、金属マグネシウムの表面に生じる水酸化物を除去する、上記<1>~<7>の何れかに記載の還元水の作製方法。
<9> 金属マグネシウムを酸化させて陰極で水素を発生させる、上記<1>~<8>の何れかに記載の還元水の作製方法。
<10> 陽極が、炭素を含む材料で形成されている、上記<9>に記載の還元水の作製方法。
<11> 上記<1>~<10>の何れかに記載の方法で作製した還元水を噴霧するスプレー装置。
<12> 上記<1>~<10>の何れかに記載の方法で作製した還元水を、液体状、固体状、粉体状、またはペースト状にして添加した食品、または化粧品。
<13> 金属マグネシウムを用いて水中で水素を発生させる還元水作製装置であって、多孔性の固相を用いることを特徴とする還元水作製装置。
<14> 電極を備え、金属マグネシウムを酸化させて陰極で水素を発生させ、還元水を作製する還元水作製装置であって、金属マグネシウム表面に生じる水酸化物を除去する固相をさらに備えることを特徴とする、還元水作製装置。
<15> 炭素を含む材料で形成されている陽極をさらに有する、上記<13>または<14>に記載の還元水作製装置。
<16> 陽極の表面を覆う被覆部材をさらに有する、上記<13>~<15>の何れかに記載の還元水作製装置。
<17> 陽極と陰極とをそれぞれ含む第1および第2の酸化還元システムを有する、上記<13>~<16>の何れかに記載の還元水作製装置。
<18> 電極を用いて水中で水素を発生させる還元水作製装置であって、炭素を含む材料で形成されている陽極を備えることを特徴とする還元水作製装置。
<19> 金属マグネシウムを用いて水中で水素を発生させる還元水作製装置であって、炭素を含む材料で形成されている陽極を備えることを特徴とする還元水作製装置。
<20> 陽極の表面を覆う被覆部材をさらに有する、上記<18>または<19>に記載の還元水作製装置。
本願発明の還元水(水素豊富水)の作製方法、および還元水(水素豊富水)作製装置では、金属マグネシウムを用いて水中で水素を発生させる。好ましい実施形態では、水中での酸化還元反応により、特に限定されるものではないが、好ましくは陽極にてマグネシウム等の金属を酸化させ、陰極で水素を発生させる。金属マグネシウムにおいては特にその使用する材料の大きさや形は限定されないが、好ましくは、0.1mmから50mm、より好ましくは1mmから5mmの粒状またはフレーク状が望ましい。この酸化還元反応で用いられる陽極としては、特にその使用する材料の種類や装置の構造は限定されないが、好ましくは、ステンレス鋼、銅、アルミニウム、鉄、金、白金、銀、チタンなどの金属や、炭素を含む材料で形成されたものである。炭素を含む材料で形成されている陽極は、水素の発生に伴い生成される水酸化物イオンを炭酸イオンに変換させ、水系内のpH値の極度の上昇を防止できる点で、特に優れている。炭素を含む材料で形成されている陽極の例として、炭素棒、炭素含有樹脂、樹脂浸透炭素などの炭素含有固相、などが使用できる。
陽極として使用される材料の重量は特に限定されないが、好ましくは重さ0.1gから1kg、より好ましくは1gから50gである。陽極として使用される材料の形状は特に限定されないが、好ましくは棒状、より好ましくは円柱である。
2.固相
本願発明の還元水(水素豊富水)の作製方法、および還元水(水素豊富水)作製装置では、多孔性の固相が用いられる。固相は、金属マグネシウムの表面に生じる水酸化物、すなわち水酸化マグネシウム等を除去することが好ましい。このような固相を用いることにより、特に、固相を陽極に接触させて用いることにより、水への溶解性の低い水酸化マグネシウム等が金属マグネシウムの表面を被覆することが防止され、より多くのマグネシウムイオンを水中に溶解させることができる。更に固相は、溶解したマグネシウムイオンとイオン結合することが好ましい。これにより水に対するマグネシウムの溶解度が上がる。このような固相を用いることにより、水素を発生させる反応が良好な状態のまま、長期間継続される。
2.(1)イオン交換作用を持つ固相の調製法
固相の材質や、固相に含まれる官能基の種類は特に限定されない。例えば、イオン交換樹脂を水中に金属マグネシウムとともに添加すると溶存水素が上昇する効果が認められるが、より好ましくは、陽イオン交換樹脂を用いる。陽イオン交換樹脂の官能基は、水中で負の電荷を有するものであれば特に限定されないが、好ましくは、スルホン酸基やカルボン酸基などが使用できる。より好ましくはスルホン酸基が使用できる。特に限定されないが、そのまま使用すると官能基の酸と金属マグネシウムとの反応により一時的に水素が過剰に発生するため、例えば、酸性官能基の塩を形成した陽イオン交換樹脂を使用することが望ましい。酸性官能基の塩を形成する中和方法としては、特に限定されないが、例えば水酸化ナトリウムを用いて塩にする。
以上のように、固相としては、多孔性のイオン交換樹脂、特に、スルホン酸基、カルボン酸基などの酸性官能基を有する陽イオン交換樹脂が好適に用いられる。特に、後述するように、2nm未満の多数の小さな穴(細孔)を有する「ミクロ多孔性」、あるいは、物質内部に50nmより大きな多数の小さな穴(細孔)を有する「マクロ多孔性」の樹脂の他にも、その中間の大きさの穴を持つ「メソ多孔性」の樹脂を使用することができる。また、非多孔性の固相であっても使用可能である。
固相の総交換容量は特に限定されないが、好ましくは0.1eq(当量)/L―R(膨潤後の樹脂の体積(L))以上、より好ましくは1.0eq(当量)/L―R(膨潤後の樹脂の体積(L))以上である。固相として添加する樹脂の量は、特に限定されないが好ましくは膨潤した樹脂の体積換算で、金属マグネシウム1gあたり0.2ml/g~500ml/g、より好ましくは2ml/g~10ml/gである。
また、固相は、金属マグネシウムと混合して使用され得る。ここで、例えば陽イオン交換樹脂である固相(乾燥重量)と、金属マグネシウムとの混合比(重量比)は、1:10~25:1であることが好ましく、より好ましくは、1:1~5:1である。
陰極については、特に材料の種類、形状は限定されない。陰極として、好ましくはステンレス鋼、銅、アルミニウム、鉄、金、白金、銀、チタンなどの金属や、炭素棒、炭素含有樹脂、樹脂浸透炭素などの炭素含有固相、より好ましくはステンレス鋼が使用できる。
上述のように、陽極に炭素を含む材料を使用して水酸化物イオンを陽極で二酸化炭素に変換させる場合、炭素粉が生じて水が汚れることがある。これを防ぐために、炭素粉の通過を遮る被覆部材で、陽極の表面を覆うことが好ましい。被覆部材として、特に限定されるものではないが、好ましくは、フィルム、紙、布、膜により、より好ましくは樹脂性のメンブレンフィルター等の多孔質のフィルム状フィルター、ガラス繊維フィルター、セロファン、濾紙などにより、炭素を含む陽極のまわりを囲い、水の汚染を防ぐ。なお、被覆部材は、水、水酸化物イオン、二酸化炭素、および炭酸イオンを通過させられることが好ましい。
還元水(水素豊富水)作製装置においては、電極をそれぞれ含む複数の酸化還元システムを有することが好ましい。電極としては、上述の陽極および陰極が使用可能である。酸化還元システムにおいては、例えば陽極と固相を外部から隔てるケースを設けても良い。このケースは、例えばプラスチックなどの不導体で形成される。ケースには、穴を形成し、水を選択的に通過させるシート状部材等により、穴を塞ぐことが好ましい。シート状部材としては、特に限定されないが、例えば、好ましくは布、濾紙、膜、紙、フィルムなどが、より好ましくはナイロンメッシュが使用できる。
単一の還元水作製装置にて複数の酸化還元システムを設けることにより、個々のシステム(回路)に通電する電流と電圧を各々別々に調整でき、還元水(水素豊富水)の溶存水素濃度とpHの微調整が可能になる。また、酸化還元システムの形状は、例えば筒状であるが、これには限定されない。
本願発明において、酸化還元反応に用いる水の種類は、特に限定されないが、好ましくは水道水、井戸水、河川の水、湖沼の水、海水、ミネラル水、蒸留水、逆浸透水より好ましくは水道水、ミネラル水などが使用できる。添加する水の量は特に限定されないが、好ましくは、例えば金属マグネシウム1gあたり0.1ml/g~1L/g、より好ましくは4ml/g~20ml/gである。反応液のpHは特に限定されていないが、好ましくはpH3~pH14、より好ましくはpH7~pH12で使用する。反応進行後の酸化還元電位は、特に限定されないが、-800mV~500mV、好ましくは-300mV~-10mVである。反応進行後の溶存水素量は、特に限定されないが、0.001~1.6重量ppm、好ましくは0.1~1.2重量ppmである。なお、本明細書では、0.005重量ppm以上の水素を含む水を水素豊富水と定める。ただし、このことは、0.005重量ppm未満の水素を含む還元水の作製方法、作製装置を、本願発明から除外するものではない。
また、酸化還元反応用の水には、特にその種類は限定されないが、必要により緩衝剤、酸化剤、還元剤、酸、アルカリ、塩、糖、吸着剤等を混合して用いることができる。
金属マグネシウムは、水と反応して水素と水酸化マグネシウムになる。この酸化還元反応の化学式を以下に示す。
上述の作製方法により作製される還元水(水素豊富水)は、例えば、スプレー装置内に充填され、噴霧されて使用される。また、還元水(水素豊富水)は、液体状のまま、あるいは、固体状、粉体状、またはペースト状に加工され、食品、または化粧品に添加される。
印加する電圧は特に限定されないが、好ましくは0.1Vから1000V、より好ましくは3Vから100Vが使用される。流す電流は特に限定されないが、好ましくは0.1mAから1000A、より好ましくは5mAから400mAが使用される。作製した還元水(水素豊富水)の形態は直接あるいはスプレーとして使用できる。反応容器は特に限定するものではないがスティック、コップ、タンク、ウォーターサーバー、交換用カセットなどが使用できる。できた水は直接飲料可能で、または、液体状、固体状、粉体状、ペースト状等の状態にして食品や化粧品として使用できる。
前記「イオン交換」とは、ある種の物質が示す、接触している電解質溶液に含まれるイオンを取り込み、代わりに自らの持つ別種のイオンを放出することで、イオン種の入れ換えを行う現象または能力を意味する。
前記「樹脂」とは、樹皮より分泌される不揮発性の固体または半固形体の物質のことである。
または、有機化学の発達により合成されるようになった、天然樹脂とよく似た性質を持つ物質のことである。
前記「イオン交換樹脂」とは、合成樹脂の一種で、分子構造の一部にイオン基として電離する構造を持つ。水などの溶媒中のイオンとイオン交換作用を示すが、その挙動はイオンに対する選択性に従う。イオン基の性質により、陽イオン交換樹脂と陰イオン交換樹脂に大別され、またその解離性により強酸・弱酸、強塩基・弱塩基に分けられる。
前記「官能基」とは、物質の化学的属性や化学反応性に注目した原子団の分類で、それぞれ特有の物性や化学反応性を示す。化学的な性質を化合物に与える原子群のことである。
前記「総交換容量」とは、一定量の官能基を持つ樹脂が保持できるイオンの総量である。
前記「当量」とは、化学反応における量的な比例関係を表す概念である。代表的なもののひとつとして物質量の比を表すモル当量がある。単位としては、Eqを用いる。
前記「中和」とは、酸と塩基を混合して、双方の性質を打ち消しあわせ、水と塩をつくることである。
前記「膨潤」とは、イオン交換樹脂に水などを加え充分に吸わせて膨らませることである。イオン交換樹脂を使用する前に行う。
前記「酸化還元」とは、化学反応のうち、反応物から生成物が生ずる過程において、原子やイオンあるいは化合物間で電子の授受がある反応のことである。
前記「多孔性」とは、活性炭に代表される吸着剤など、分子を取り込み吸着する役割を果たす物質などが持つ、物質内部に多数の小さな穴(細孔)を有する状態を意味する。
前記「ミクロ多孔性」とは、一般に、物質内部に2nm未満の多数の小さな穴(細孔)を有する状態である。
前記「マクロ多孔性」とは、一般に、物質内部に50nmより大きな多数の小さな穴(細孔)を有する状態である。
前記「メソ多孔性」とは、一般に、物質内部に2nmより大きく、50nmより小さな多数の小さな穴(細孔)を有する状態である。
前記「酸化還元電位」とは、ある酸化還元反応系における電子のやり取りの際に発生する電位(正しくは電極電位)のことである。物質の電子の放出しやすさ、あるいは受け取りやすさを定量的に評価する尺度でもある。単位はボルトを用いる。
前記「緩衝剤」とは、緩衝作用のある溶液のことを言う。通常、単に緩衝液とだけいう場合は、水素イオン濃度に対する緩衝作用のある溶液を指す。
前記「不織布」とは、通常の布のように繊維を撚って糸にしたものを織ることなく、繊維を熱・機械的または化学的な作用によって接着または絡み合わせる事で布にしたものを指す。
前記「逆浸透水」とは、濾過膜の一種であり、水を通しイオンや塩類など水以外の不純物は透過しない性質を持つ膜を通した水のことである。
前記「炭素含有樹脂」とは、樹脂に炭素粉を練りこみ成形したものである。伝導性を持ち、且つ強度が優れているなどの特徴を持つ。
前記「樹脂浸透炭素」とは、炭素棒などの固相表面から樹脂を浸透させたものである。伝導性を持ち、且つ強度が優れているなどの特徴を持つ。
「ゲル」とは、高分子の網が液体を閉じこめている材料である。高分子が寄り添うだけで結びつきが弱いのが物理ゲルで、ゼリーや寒天が代表的である。高分子を化学結合させたのが化学ゲルで、吸水材やコンタクトレンズなどがある。「重合体」とは、複数の単位構造(単量体)が重合する(結合して鎖状や網状になる)ことによってできた化合物のことである。このため、一般的には高分子の有機化合物である。「共重合体」とは、2種類以上の単位構造(単量体)からなる重合体のことを特に共重合体と言う。「担体」とは、吸着や触媒活性を示す物質を固定する土台となる物質のことである。担体自体は、化学的に安定したもので、目的操作を阻害しないものが望ましい。「水素豊富水」とは、水素分子(水素ガス)を多く含む水のことである。水素分子が水に溶けて水素イオンとなることは無い為、水素分子がpHに直接影響することは無い。「電気分解」とは、化合物に電圧をかけることにより電気化学的に酸化還元反応を引き起こし、化合物を化学分解する方法である。略して電解ともいう。「電解隔膜」とは、電気分解で、両極の反応生成物が混合して副反応をするのを防ぐために、両極間に置く多孔質の隔壁である。
200CT NA(登録商標)は、スチレン・ジビニルベンゼン共重合体のMR構造を担体として持つ強酸性イオン交換樹脂であり、官能基としてスルホン酸が結合している。
IR120B NA(登録商標)も類似の構造を持つが、ゲル構造を持つ担体である。
また、200CT NA(登録商標)とIR120B NA(登録商標)は使用する時点で、各々水酸化ナトリウムで塩として中和されている。
なお、マグネシウム以外の金属、例えば、鉄、亜鉛等も水素発生のために使用できるものの、反応性、水素発生の効率、および安全性の観点から、金属マグネシウムが特に適している。
200CT NA(登録商標)は、担体に官能基としてスルホン酸が、IRC76(登録商標)は、担体に官能基としてカルボン酸が、IRA400J Cl(登録商標)は、担体に官能基として第4アンモニウム塩基が、そしてIRA67(登録商標)は、担体に官能基として3級アミンが結合している。200CT NA(登録商標)はスチレン・ジビニルベンゼン共重合体を担体として有し、IRC76(登録商標)はポリアクリル共重合体を担体として有し、IRA400J Cl(登録商標)はスチレン・ジビニルベンゼン共重合体を担体として有し、IRA67(登録商標)はアクリル・ジビニルベンゼン共重合体を担体として有する。また、200CT NA(登録商標)とIRA400JCl(登録商標)は、使用する時点で、各々水酸化ナトリウムと塩酸で塩として中和されている。IRC76(登録商標)とIRA67(登録商標)は、100mlのビーカーに膨潤した樹脂20mlをとり、100mlの水道水を入れ各々1規定になるように水酸化ナトリウムと塩酸を添加し、一晩、中和操作を実施した。これらのサンプルを水道水で良く洗浄して、pHを、塩酸や水酸化ナトリウムで中性から弱アルカリとし、最後に各々金属マグネシウム5gと水道水を加え最終的に100mlとして実験を開始した。
Claims (20)
- 金属マグネシウムを用いて水中で水素を発生させる方法において、多孔性の固相を用いることを特徴とする還元水の作製方法。
- 固相が、イオン交換作用を有する、請求項1に記載の還元水の作製方法。
- 固相が酸性の官能基を有する、請求項1または請求項2に記載の還元水の作製方法。
- 固相がスルホン酸基を有する、請求項1~請求項3の何れか一項に記載の還元水の作製方法。
- 固相がカルボン酸基を有する、請求項1~請求項3の何れか一項に記載の還元水の作製方法。
- 固相が樹脂である、請求項1~請求項5の何れか一項に記載の還元水の作製方法。
- 固相がイオン交換樹脂である、請求項1~請求項6の何れか一項に記載の還元水の作製方法。
- 固相が、金属マグネシウムの表面に生じる水酸化物を除去する、請求項1~請求項7の何れか一項に記載の還元水の作製方法。
- 金属マグネシウムを酸化させて陰極で水素を発生させる、請求項1~請求項8の何れか一項に記載の還元水の作製方法。
- 陽極が、炭素を含む材料で形成されている、請求項9に記載の還元水の作製方法。
- 請求項1~請求項10の何れか一項に記載の方法で作製した還元水を噴霧するスプレー装置。
- 請求項1~請求項10の何れか一項に記載の方法で作製した還元水を、液体状、固体状、粉体状、またはペースト状にして添加した食品、または化粧品。
- 金属マグネシウムを用いて水中で水素を発生させる還元水作製装置であって、多孔性の固相を用いることを特徴とする還元水作製装置。
- 電極を備え、金属マグネシウムを酸化させて陰極で水素を発生させ、還元水を作製する還元水作製装置であって、金属マグネシウム表面に生じる水酸化物を除去する固相をさらに備えることを特徴とする、還元水作製装置。
- 炭素を含む材料で形成されている陽極を有する、請求項13または請求項14に記載の還元水作製装置。
- 陽極の表面を覆う被覆部材をさらに有する、請求項13~請求項15の何れか一項に記載の還元水作製装置。
- 陽極と陰極とをそれぞれ含む第1および第2の酸化還元システムを有する、請求項13~請求項16の何れか一項に記載の還元水作製装置。
- 電極を用いて水中で水素を発生させる還元水作製装置であって、炭素を含む材料で形成されている陽極を備えることを特徴とする還元水作製装置。
- 金属マグネシウムを用いて水中で水素を発生させる還元水作製装置であって、炭素を含む材料で形成されている陽極を備えることを特徴とする還元水作製装置。
- 陽極の表面を覆う被覆部材をさらに有する、請求項18または請求項19に記載の還元水作製装置。
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- 2011-10-31 CN CN201180069230.8A patent/CN103562143A/zh active Pending
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CN103562143A (zh) | 2014-02-05 |
KR20140016939A (ko) | 2014-02-10 |
JP6132418B2 (ja) | 2017-05-24 |
US20140023724A1 (en) | 2014-01-23 |
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