HK1172602B

HK1172602B - Device for selectively hydrogenating biocompatible solution

Info

Publication number: HK1172602B
Application number: HK12113322.8A
Authority: HK
Inventors: 佐藤文武; 濑尾知树; 黑川亮介; 佐藤文平; 内藤达也; 柳原纪之; 佐藤洋平; 佐藤洋子
Original assignee: 水株式会社
Priority date: 2010-07-14
Filing date: 2011-07-12
Publication date: 2014-01-30

Description

Device for selectively adding hydrogen to biological application liquid

Technical Field

The present invention relates to an apparatus for selectively adding hydrogen to a biological application liquid.

Background

As a method for producing a hydrogen-containing biological application liquid, a method using a domestic hydrogen electrolysis water generator and a method of bringing a metal piece of metal magnesium as a hydrogen generator into contact with a biological application liquid are known (japanese patent application laid-open No. 2007-167696).

Prior art documents

Patent document 1: japanese patent laid-open No. 2007-

Disclosure of Invention

Problems to be solved by the invention

In many cases, when a hydrogen generating agent is used to obtain a hydrogen-containing biological fluid, the hydrogen generating agent changes the characteristics of the biological fluid when dissolving hydrogen molecules in the biological fluid. For example, when the hydrogen generator is metallic magnesium, magnesium ions are eluted in the biological fluid and the pH thereof is made to be alkaline in the hydrogen generation according to the following formulas (1) and (2).

Mg＋2H₂O→Mg（OH）₂+＋H²… type (1)

Mg（OH）₂₊→Mg²⁺＋2OH^-… type (2)

However, it is basically undesirable to change the composition structure of the living organism applicable fluid which has been naturally or artificially composed before and after the hydrogen generation reaction. The change of the components causes the change of the taste of the biological application liquid such as tea, mineral water, etc.

Therefore, a production tool for hydrogen-containing biological fluid that does not change the composition structure of the biological fluid is desired.

In the food hygiene act, only additives that are permitted to come into contact with food are recognized as "food additives".

However, when a hydrogen water is to be produced using a hydrogen generating agent, magnesium, hydride, and the like, which are hydrogen generating agents, are not considered as food additives, and therefore both violate the food hygiene law.

Means for solving the problems

Therefore, in the case of producing hydrogen water using a hydrogen generating agent as an essential component, it is necessary to store the hydrogen generating system including the hydrogen generating agent in a container such as plastic so that the hydrogen generating system does not come into contact with food (biological application liquid) at all.

The hydrogen generation system container is provided with an exhaust port for discharging hydrogen gas. The exhaust port is installed so as to be located in the upper gas phase portion of the closed vessel (in order to prevent water from flowing in).

The hydrogen gas from the exhaust port of the hydrogen generating agent container in the closed container is sent to the gas phase part of the closed container to replace the gas in the gas phase part with the hydrogen gas, and the gas phase internal pressure and the hydrogen gas concentration are increased.

The high-concentration hydrogen gas under the pressure is dissolved into the liquid with the passage of time to generate high-concentration hydrogen water, thereby solving the problem.

Alternatively, a hydrogen generating system containing a hydrogen generating agent such as magnesium metal as an essential component is accommodated in a hydrogen bubble forming body having a gas-liquid separation section which is devised to release hydrogen gas but to substantially prevent water from flowing in and/or release hydrogen gas but to substantially prevent water from flowing out, and the hydrogen generating agent is reacted with hydrogen generating water in the hydrogen bubble forming body, whereby hydrogen gas generated from the hydrogen bubble forming body is fed into a gas phase section of a closed vessel accommodating a living organism applicable liquid without substantially allowing the hydrogen generating water used for the hydrogen generating reaction to flow out to the living organism applicable liquid, to obtain a hydrogen-containing living organism applicable liquid, thereby solving the problem. Then, the closed container is oscillated to dissolve the high-pressure and high-concentration hydrogen gas in the gas phase into the biological application liquid, thereby obtaining a high-concentration or supersaturated hydrogen-containing biological application liquid.

Effects of the invention

By supplying hydrogen to the living organism applicable liquid by this method, the living organism applicable liquid containing hydrogen can be obtained without changing the characteristics of the living organism applicable liquid. In addition, by using this method, a high-concentration hydrogen beverage can be easily produced without changing the flavor of any beverage, regardless of the place such as home, work, street, and store.

Drawings

Fig. 1A is a plan view and a front view showing a gas-liquid separation section according to an embodiment of the present invention.

Fig. 1B is a sectional view showing a gas-liquid separation section according to an embodiment of the present invention.

Fig. 2 is a front view showing an apparatus for selectively adding hydrogen, in which the gas-liquid separation unit shown in fig. 1 is mounted on a hydrogen bubble forming body.

Fig. 3 is a front view showing another example of the apparatus for selectively adding hydrogen, in which the gas-liquid separation unit shown in fig. 1 is mounted on a hydrogen bubble forming body.

Detailed Description

Hereinafter, embodiments of the present invention will be described.

In the present invention, the biological application liquid refers to a liquid to be dissolved by the use of the present invention, such as water or an aqueous solution, which is applied to a living body. The biological liquid includes drinks such as drinking water, tea, and coffee, in addition to water. The hydrogen-containing biological application liquid obtained by dissolving hydrogen in the biological application liquid is applied to a living body by inhalation (spraying), drinking, injection, or the like, but is not limited thereto. The hydrogen-containing biological application liquid and the highly concentrated or supersaturated hydrogen-containing biological application liquid contain hydrogen as an active ingredient, and the active ingredient is mainly to suppress oxidative stress, but the present invention is not limited thereto.

In the present invention, the hydrogen generator means a substance for generating hydrogen. A metal having a higher ionization tendency than hydrogen, a hydrogenated compound containing a hydrogenated metal, or the like generates hydrogen by contacting with water, and belongs to the hydrogen generator. In view of the advantage of reactivity with water, metallic calcium, calcium hydride, metallic magnesium, magnesium hydride, and the like are preferably used. In view of safety of the reaction product and the like, metallic magnesium is particularly preferably used.

In the present invention, the hydrogen generating water refers to a liquid that generates hydrogen in the hydrogen bubble forming body by being brought into contact with a hydrogen generating agent. Such hydrogen generation water includes tap water, purified water, ion-exchanged water, distilled water, pure water, RO water, and the like, but is not limited thereto. The biological application liquid itself may be used as water for hydrogen generation. The hydrogen generating water of the present invention can be used as long as it is a water-containing liquid regardless of the content, hardness, and liquid properties.

The hydrogen generating system container according to the present invention is characterized in that the hydrogen generating system is isolated from the living organism applicable fluid, and hydrogen gas generated in the hydrogen generating system container is sent to the living organism applicable fluid through an exhaust port of the hydrogen generating system container. The apparatus of the present invention including the hydrogen generating system container can be housed in the closed container as a device separate from the closed container housing it, or can be housed in the closed container as a structural part previously housed in the closed container.

The hydrogen bubble forming body of the present invention is characterized in that the hydrogen generating system is isolated from the living organism applicable fluid, and hydrogen gas generated in the hydrogen bubble forming body is sent to the living organism applicable fluid through the gas-liquid separation section of the hydrogen bubble forming body. The apparatus of the present invention including the hydrogen bubble forming body can be housed in the closed container as a device separate from the closed container housing it, or can be housed in the closed container as a structural portion previously incorporated in the closed container.

Such a gas-liquid separation section is characterized by, for example, including a valve (including a check valve and a ball valve), a gas permeable membrane, and the like as an element or a material, and thus, it is devised to release hydrogen gas generated by a contact reaction between a hydrogen generation system and hydrogen generation water while substantially preventing the hydrogen generation water from flowing out and/or preventing the biological fluid from flowing in.

As such a method, for example, there is a method of preventing the inflow of the living organism applicable liquid into the hydrogen bubble forming body by providing a valve in the gas-liquid separation section. With this arrangement, the water flowing into the hydrogen bubble forming body can be prevented from flowing out again to the living organism applicable fluid at the time of oscillation or the like, and the hydrogen gas formed in the hydrogen bubble forming body can be released to the living organism applicable fluid. More specifically, the valve provided in the gas-liquid separation section is an open-close type valve which separates the inside and the outside of the hydrogen bubble forming body and which is opened by the gas pressure of hydrogen gas generated in the inside of the hydrogen bubble forming body by the reaction between the hydrogen generating system and the water for hydrogen generation, thereby discharging hydrogen gas to the outside of the hydrogen bubble forming body, and which is closed naturally or manually by gravity, hydraulic pressure outside the hydrogen bubble forming body, or the like after the discharge of hydrogen gas, and is characterized in that the living organism applicable liquid outside the hydrogen bubble forming body is not substantially flowed into the inside of the hydrogen bubble forming body except when the hydrogen gas is discharged.

Fig. 1 shows an example of a gas-liquid separation section using such an opening/closing valve. The gas-liquid separation section is composed of an open-close valve (a) and a plastic concave element (b) into which the valve is incorporated. The open-close type valve has one shaft part (a-2) extending from an umbrella-shaped head part (a-1), and an annular protrusion (a-3) surrounding the shaft part is processed in the middle of the shaft part. The concave member is further provided with three fan-shaped holes (b-2) so as to surround a center hole (b-1) formed in the center of the bottom surface thereof, and a rim (b-3) for hooking the head of the valve is formed in the peripheral edge portion of the bottom surface. The bottom surface is an area of an extent just to accommodate the head portion (a-1) of the valve, and when the head portion (a-1) of the valve is accommodated, the shaft portion (a-2) of the valve passes through the recess member by passing through the center hole (b-1) opened at the center portion, but the annular protrusion (a-3) surrounding the shaft portion cannot easily pass through due to its size. However, the valve (a) and the concave member (b) can be combined by pulling the shaft portion (a-2) which has passed through the center hole (b-1) provided in the center portion of the bottom surface of the concave member downward with a force, and passing the annular projection (a-3) which surrounds the shaft portion of the valve through the hole (b-1) in the bottom surface while deforming.

When the pressure of the hydrogen gas generated inside the hydrogen bubble forming body rises, the head portion of the open-close valve located at the bottom of the concave element is pushed open to discharge the hydrogen gas, but the annular projection surrounding the shaft portion is hooked on the center hole provided at the center portion of the bottom surface of the concave element, so that the open-close valve does not fall off from the concave element even when the pressure of the hydrogen gas during the exhaust is applied.

In this case, the amount of the hydrogen generation water introduced into the hydrogen bubble forming body can be further reduced, and the hydrogen generation water can be prevented from flowing out to the living organism applicable liquid even when the hydrogen gas is released from the valve.

As a criterion of the amount of the water for generating hydrogen to be used, in the case where the water for generating hydrogen is introduced into the hydrogen bubble forming body accommodating the hydrogen generating system and then the hydrogen generating system is removed (including a covering material when the hydrogen generating system is covered with a covering material or the like described later), the amount of the water for generating hydrogen remaining in the hydrogen bubble forming body is desirably 10cc or less, preferably 5cc or less, more preferably 3cc or less, and particularly preferably 1cc or less. In order to prevent such surplus hydrogen generation water from flowing out, it is desirable to include water-absorbing materials or materials such as water-absorbing beads, ion exchange resins (dry ion exchange resins are more preferred because of their high water absorption properties as described later), water-absorbing paper, hyaluronic acid, and polyacrylic acid in the hydrogen bubble forming body and a covering material described later.

In addition, a part or the whole of the hydrogen bubble forming body can be constituted by such a gas-liquid separating portion. It is desirable that the material other than the gas-liquid separation portion provided in the hydrogen bubble forming body is a material which is less permeable to water and less corroded by water, such as an acrylic resin.

As another method, for example, a method is included in which a hydrogen gas permeable membrane is provided in the gas-liquid separation section, the membrane allowing water to flow into the hydrogen bubble forming body without allowing water to flow out of the hydrogen bubble forming body, that is, the membrane allowing water to flow in and out to be irreversibly controlled. By bringing the apparatus for producing hydrogen-containing living organism applicable liquid having such a gas-liquid separation section into contact with the living organism applicable liquid, a part of the living organism applicable liquid flows into the hydrogen bubble forming body through the gas-liquid separation section. The inflowing organism application liquid is used as hydrogen generation water to react with a hydrogen generation system in the hydrogen bubble forming body to generate hydrogen. The generated hydrogen gas is released from the gas-liquid separation section to the biological application liquid, but the hydrogen-generating water is blocked by the membrane and does not flow out to the biological application liquid.

In the present invention, in order to achieve perfect isolation between the living organism applicable liquid and the hydrogen generating system, a solid component such as a hydrogen generating agent contained in the hydrogen generating system may be further covered with a covering material such as a nonwoven fabric. This covering material is characterized by allowing hydrogen and water to permeate therethrough, but not allowing a hydrogen generating system or reaction residues thereof to permeate therethrough. The pore size of such a covering material is desirably 1000 μm or less, preferably 500 μm or less, more preferably 150 μm or less, and particularly preferably 50 μm or less.

Further, the average particle size of the hydrogen generating agent such as metallic magnesium of the present invention is preferably a particle size that does not permeate outside the covering material and can increase the activity by microparticulation. For example, the average particle diameter of the hydrogen generator is desirably 3000 μm or less, preferably 1000 μm or less, more preferably 500 μm or less, and particularly preferably 250 μm or less.

The hydrogen generating system of the present invention may contain a hydrogen generating agent, and agents for promoting a hydrogen generating reaction, such as a metal ion chelating agent and a pH adjuster.

Such metal ion chelating agents include the following: completely or substantially insoluble in water, and generates a substance having a property of adsorbing metal ions inside the hydrogen bubble forming body or the covering material. An insoluble or hardly soluble metal ion chelating agent such as a cation exchange resin is preferably used. Wherein metal ions are adsorbed and hydrogen ions (H) are released⁺) The hydrogen ion type cation exchange resin (2) comprising an acidic cation exchange resin having a sulfonic acid group as an exchange group or an acidic cation exchange resin having a carboxylic acid group as an exchange group also functions as a pH adjuster, and is therefore more preferred.

The pH regulator of the present invention comprises: citric acid, adipic acid, malic acid, acetic acid, succinic acid, gluconic acid, lactic acid, phosphoric acid, hydrochloric acid, sulfuric acid, etc. have a function of supplying hydrogen ions (H)^＋) To inhibit (neutralize or prevent the formation of) hydroxide ions (OH)^-) And a substance that removes hydroxide ions by undergoing hydrolysis to form an insoluble hydroxide. It is preferable to use a pH adjuster in which an ore or the like containing aluminum ions is hydrolyzed to form an insoluble hydroxide. Among them, alum such as aluminum ammonium sulfate is more preferable because it is hydrolyzed to generate insoluble aluminum hydroxide and also functions as a metal ion chelating agent (coagulant) for magnesium ions and calcium ions.

As described above, the hydrogen ion type cation exchange resin and alum are preferable as a chemical having both a function as a metal ion chelating agent and a function as a pH adjuster.

In order to suppress deterioration of the hydrogen generating agent with time, it is preferable that the number of hydrates and the water content of the substance contained in the hydrogen generating system such as the metal ion chelating agent and the pH adjuster are small. That is, the number of hydration is desirably 3 hydrates or less, preferably 2 hydrates or less, more preferably 1 hydrate or less, and particularly preferably anhydrous or anhydrous. The water content is desirably 40% by weight or less, preferably 30% by weight or less, more preferably 20% by weight or less, and particularly preferably 15% by weight or less.

In the present invention, the high-concentration hydrogen-containing biological use solution includes a hydrogen-containing biological use solution having a dissolved hydrogen concentration of 0.1ppm or more, preferably 1.0ppm or more. In the present invention, the supersaturated hydrogen-containing biological use solution includes a dissolved hydrogen concentration at which the dissolved hydrogen concentration is not less than the solubility at normal temperature and pressure, and includes a high-concentration hydrogen-containing biological use solution of not less than 1.6ppm, not less than 2.0ppm, not less than 3.0ppm, not less than 4.0ppm, not less than 5.0ppm, not less than 6.0ppm, not less than 7.0ppm, not less than 8.0ppm, not less than 9.0ppm, and not less than 10.0 ppm.

In the closed container for containing the biological fluid, the apparatus for selectively adding hydrogen to the biological fluid, which contains the hydrogen generating system in the hydrogen bubble forming body according to the present invention, may be provided in the biological fluid, in the air layer of the closed container, or outside the closed container.

In the hydrogen bubble forming body, hydrogen gas generated by the reaction between the hydrogen generating system and the hydrogen generating water is released to the closed container containing the living organism applicable liquid through the gas-liquid separation part of the hydrogen bubble forming body, and a high-pressure and high-concentration hydrogen gas phase is formed. Further, the applicant found that even when the apparatus for selectively adding hydrogen to a living organism applicable liquid of the present invention is installed in a living organism applicable liquid, the generated hydrogen molecules are first transferred to the air in the closed vessel without being dissolved in the living organism applicable liquid.

Further, the applicant found that, in the case where the hydrogen generating agent is contained in the hydrogen bubble forming body and is disposed in the living organism applicable fluid, the amount of hydrogen dissolved in the living organism applicable fluid after the introduction is further reduced, as compared with the case where the hydrogen generating agent is not contained in the hydrogen bubble forming body and is introduced in the living organism applicable fluid in an exposed state.

That is, hydrogen molecules generated from the hydrogen generating agent not accommodated in the hydrogen bubble forming body are dissolved directly in the living organism applicable liquid, forming clusters (clusters) or fine bubbles, and on the other hand, when the hydrogen molecules are discharged to the living organism applicable liquid through the gas-liquid separation portion of the hydrogen bubble forming body, the hydrogen bubble forming body functions as a kind of barrier against hydrogen gas, and therefore the hydrogen molecules are accumulated in a proper amount in the vicinity of the inner wall of the gas-liquid separation portion and then discharged as hydrogen bubbles from the gas-liquid separation portion. In other words, when hydrogen molecules are released into the biological application liquid, the hydrogen molecules are released as hydrogen gas bubbles already having a certain size.

This can also be observed visually. For example, when the apparatus for selectively adding hydrogen to a biological fluid of the present invention is placed in a closed container for containing the biological fluid, and the container is placed in a horizontal state for a while, hydrogen gas generated in the hydrogen bubble forming body gradually increases the volume of the hydrogen gas phase while intermittently releasing the hydrogen bubbles from the gas-liquid separation section. In other words, since the bubble size of the evolved hydrogen gas is large, it rises in water and rapidly migrates to the gas phase of the closed vessel.

In general, not limited to hydrogen molecules, it is considered that, among those skilled in the art of producing gas solutions for certain industrial applications, it is important to delay the rising rate of bubbles toward the gas phase by reducing the bubble size of gas as much as possible in order to produce a gas solution with a high concentration. The micro-bubbling and further nano-bubbling of various industrial gases including hydrogen, oxygen, or ozone is still considered to be one of the main technical problems in the art at the time of filing the present application.

On the other hand, the present inventors have found that, in a case where a consumer wants to obtain a hydrogen-containing biological application liquid having a high concentration at the time of use in various places including home, work, street, and store, it is more desirable to first form a hydrogen gas phase in a closed container and increase the internal pressure of the container, and then appropriately oscillate the closed container to recover the hydrogen gas in the gas phase, than to directly dissolve hydrogen molecules in a biological application liquid in the closed container containing a biological application liquid including drink water, tea, coffee, and the like.

In fact, in the experiments by the present inventors, when the living organism applicable liquid provided in the closed vessel without containing the metal magnesium, i.e., the hydrogen generating agent, in the hydrogen bubble forming body, the dissolved hydrogen concentration of the living organism applicable liquid after 10 minutes had elapsed was increased to about 0.7ppm, but even if the closed vessel was shaken thereafter, the dissolved hydrogen concentration was increased only to about 0.9ppm (about 1.3 times). On the other hand, when the same amount of magnesium metal, i.e., a hydrogen generating agent, was contained in the living organism applicable liquid in the closed vessel in which the hydrogen bubble forming body was installed, the dissolved hydrogen concentration of the living organism applicable liquid after 10 minutes had passed was only 0.2ppm in the zone, and then the dissolved hydrogen concentration was increased to about 3.0ppm (about 15 times) by shaking the closed vessel.

Therefore, in order to increase the dissolved hydrogen concentration of the hydrogen-containing biological application liquid, it is desirable to store the apparatus for selectively adding hydrogen to the biological application liquid, which is formed by storing the hydrogen generating system and the water for hydrogen generation in the hydrogen bubble forming body according to the present invention, in a closed container and appropriately oscillate the closed container.

In this case, the closed container of the present invention includes a container contrived so that the contents of the container do not come into contact with the atmosphere. Containers with covers, such as plastic bottles, aluminum bottles and the like with covers, belong to closed containers. It is desirable that the containment vessel have a hand-held form and capacity to be easily hand-held and oscillated by a person. The volume of the closed container is desirably 2L or less, preferably 1L or less, and particularly preferably 0.5L or less, but the closed container is not limited thereto.

As a material of the closed container, a container having low hydrogen permeability is preferable. The lower the hydrogen permeability, the less the generated hydrogen will escape out of the container system.

In the present invention, the hydrogen permeability of the closed container was measured as follows. That is, with reference to the method described in japanese patent application No. 2009-221567, hydrogen-dissolved water that stably maintains a substantially saturated concentration (1.6 ppm at 20 ℃ · 1 pressure) was produced in a volume 20 times as large as the internal volume of a closed container to be measured, and the closed container filled with purified water (activated carbon-treated water obtained by treating japanese rattan city tap water with an activated carbon column, or the like) was immersed in the hydrogen-dissolved water for 5 hours.

Then, the dissolved hydrogen concentration of the purified water is measured, and the sealed container having a dissolved hydrogen concentration of 1000ppb or less, preferably 500ppb or less, more preferably 100ppb or less, and particularly preferably 10ppb or less is one of the containers having low hydrogen permeability of the present invention.

The closed container is desired to have pressure resistance capable of withstanding an increase in internal pressure due to hydrogen generation. A pressure-resistant vessel capable of withstanding an internal pressure of 0.11MPa, preferably 0.4MPa, more preferably 0.5MPa, and particularly preferably 0.8MPa on an absolute pressure scale is desired. Preferably, a plastic bottle for carbonated beverage or the like is used. It is desirable for the closed vessel to have a mechanism (vent groove) at the mouth portion that releases the pressure in the middle of opening the cap to enable safe opening of the bottle stopper.

In the present invention, the oscillation means bringing the biological application liquid in the closed container into contact with hydrogen in a gas phase by applying physical impact to the closed container and replacing a dissolved gas such as dissolved oxygen in the biological application liquid with hydrogen. The oscillation of the present invention includes not only natural oscillation using a hand but also artificial oscillation using a machine. The oscillation by an oscillator, a stirrer, an ultrasonic wave generator, or the like is such artificial oscillation.

In order to further accumulate hydrogen gas in the gas phase of the closed vessel, it is desirable that the oscillation start be started after 1 minute, preferably 2 minutes, more preferably 4 minutes, still more preferably 8 minutes, and particularly preferably 10 minutes has elapsed after the apparatus for selectively adding hydrogen of the present invention is installed in the closed vessel.

In addition, typical examples of natural oscillation according to the present invention are as follows. That is, a japanese male in the thirties with an average physique holds the abdomen of the closed container in a handful manner, and reciprocates 120 times at a rhythm of 2 times/second by moving only the wrist so that the cover draws a semicircular arc above the wrist.

In order to promote dissolution of high-pressure and high-concentration hydrogen gas into the biological application liquid, the oscillation time is desirably 5 seconds or longer, preferably 10 seconds or longer, more preferably 15 seconds or longer, and still more preferably 30 seconds or longer under natural oscillation.

In addition, in view of ease of handling of the oscillation, it is desirable to provide a headspace in the closed container in a volume of 15% or less, preferably 10% or less, particularly preferably 5% or less of the container volume after filling the biological fluid.

Further, the oscillation is preferably an oscillation in which the dissolved hydrogen concentration of the biological use solution is increased to 2 times or more, preferably 3 times or more, more preferably 4 times or more, 5 times or more, 6 times or more, 7 times or more, 8 times or more, 9 times or more, and further preferably 10 times or more, in order of the dissolved hydrogen concentration before the oscillation, when the apparatus for selectively adding hydrogen to the biological use solution of the present invention is set in the biological use solution and the oscillation is performed.

In order to obtain a hydrogen-containing biological fluid of higher concentration such as a supersaturated hydrogen-containing biological fluid of 1.6ppm or more, it is preferable that the internal pressure of the closed container before the oscillation is in a state of atmospheric pressure or more. The solubility of hydrogen molecules in the living organism applicable solution increases with the increase in the internal pressure of the sealed container to which the generated hydrogen molecules are applied, and in the near future, exceeds the solubility at normal temperature and normal pressure. In examples and the like described later, the reason why the closed container having the hydrogen generating system is left for a certain period of time is to pressurize the closed container from the inside by the generated hydrogen gas, and to further promote the dissolution of hydrogen molecules into the hydrogen-containing living organism applicable liquid by appropriately oscillating the closed container under pressurization.

However, an insoluble polymer substance having a metal ion chelating function and a pH adjusting function such as the above-mentioned hydrogen ion type cation exchange resin can constitute a compact hydrogen generating system in which three functions of hydrogen generation, metal ion chelating, and pH adjusting are closely related to each other by combining with a hydrogen generating agent including a metal having a higher ionization tendency than hydrogen such as metallic magnesium, and a hydrogenation metal. Hereinafter, a hydrogen generating system comprising metal magnesium and a hydrogen ion type cation exchange resin will be described as an example.

Generally, when magnesium metal is brought into contact with a living organism application liquid phase, hydrogen molecules and magnesium hydroxide are produced according to the following formula (1).

Mg＋2H₂O→Mg（OH）₂₊＋H²… type (1)

The reaction mechanism is considered to be electron emission from magnesium metal,

Mg→Mg^2＋＋2e^-… type (2)

Electrons derived from metallic magnesium are reduced with water molecules to generate hydrogen molecules and hydroxide ions and

2H₂O＋2e^－→2OH^－＋H²… type (3)

Electrons from metallic magnesium are used to generate hydrogen molecules by reducing hydrogen ions

2H^＋＋2e^－→H²… type (4)

Such a motif reacts.

Here, in the case where the hydrogen ion type cation exchange resin exists adjacent to metallic magnesium, magnesium ions released according to the formula (2) are adsorbed to the hydrogen ion type cation exchange resin, and hydrogen ions are released from the hydrogen ion type cation exchange resin. Therefore, the electrons emitted according to the formula (2) preferentially reduce the hydrogen ions located nearby compared to the reducing water molecules.

In this way, in the hydrogen generating system of the present invention, hydrogen is generated in accordance with the formula (4) of the hydrogen generating reaction in which hydroxide ions are not generated, in preference to the formula (3) of the hydrogen generating reaction in which hydroxide ions are generated. Therefore, the hydrogen generation reaction is easily promoted because the magnesium ions and the hydroxide ions tend to be kept in a state of being reduced all the time in the system.

In the present invention, the state in which the component structure of the biological fluid is not changed is not limited to this, and includes, for example, the case in which the entire hardness or pH of the biological fluid is not changed.

Here, the state in which the hardness of the entire biological application liquid is not changed is not limited to this, and includes, for example, the following states.

Namely, the following states and the like are provided: a device for producing a non-destructive high-concentration hydrogen solution according to the present invention is provided in a biological application liquid in a plastic bottle for carbonated beverages (about 530cc volume when filled to the mouth) filled with a biological application liquid in a plastic bottle for carbonated beverages (about 530cc volume when the bottle is left laid aside for 10 minutes) filled with a purified water (purified water obtained by treating Japanese Tenze city tap water through an activated carbon column) obtained by dechlorinating tap water and having a total hardness (Ca hardness + Mg hardness) of about 55ppm to 65ppm, and the total hardness of the solution after a typical natural oscillation (120 times of a 2-time round trip/second round trip with the abdomen of the plastic bottle held in the handy hand and the cover moved left and right so as to form a semicircular arc over the wrist) is (total hardness of raw water-25 ppm) to (total hardness of raw water + 25 ppm), preferably (total hardness of raw water-15 ppm) to (total hardness of raw water-15 ppm) + total hardness of raw water), Particularly preferably (total hardness of raw water-10 ppm) to (total hardness of raw water + 10 ppm).

Here, the state in which the pH of the biological application liquid is not changed is not limited to this, and includes, for example, the following states.

Namely, the following states and the like are provided: a device for producing a non-destructive high-concentration hydrogen solution according to the present invention is provided in a biological application liquid in a plastic bottle for carbonated beverages (about 530cc volume when filled to the mouth) filled with a biological application liquid of about 515cc of a purified water (purified water obtained by treating tap water from Japan Tenze city with an activated carbon column) having a pH of about 7.0 to 7.8 and obtained by dechlorinating tap water, the pH of the solution after a typical natural shaking (holding the middle abdomen of the plastic bottle in a handy state, and moving the wrist to the left and right to draw a semicircular arc by moving the cap over the wrist so that the bottle is left and right to perform 120 reciprocal shaking operations at a rhythm of 2 reciprocal/second) after the bottle is left to stand for 10 minutes is in the range of (pH of raw water-1.5) to (pH + 1.5 of raw water), preferably (pH of raw water-1.0) to (pH + 1.0 of raw water), and particularly preferably (pH of raw water-0.5 ppm) to (pH + 0.5 of raw water).

Examples

Hereinafter, examples of the present invention will be described. In the present application, unless otherwise specified, the pH meters (including the thermometers) used for measuring various physical property values are those manufactured by horiba, ltd. (body model "D-13" and probe model "9620-10D") and those manufactured by DKK, east asia (trade name, "DHDI-1", electrode (probe) model "HE-5321" and relay model "DHM-F2").

The calcium hardness and the magnesium hardness were measured by a calcium-magnesium reagent colorimetry using a water quality analyzer "DR/4000" (manufactured by HACH Co.).

Example 1 (shown in FIG. 2) A hydrogen generating system (c-1) containing 300MG of magnesium metal (MG 100: Kanto metal, K.K.) as a hydrogen generating agent and 1500MG of a hydrogen Ion type cation Exchange Resin (a Resin obtained by heat-drying DIAION Ion Exchange Resin SK1 BH: Mitsubishi chemical Corporation, which is a product of strong acid Ion Exchange Resin H type on the market) was wrapped in a nonwoven fabric (Precise Regulara C5160: Asahi Kasei Co., Ltd.) (c-forming body 2) and heat-sealed, and then the nonwoven fabric was housed together with a cylindrical hydrogen bubble (c-3) made of an acrylic Resin. The apparatus for selectively adding hydrogen to the living organism applicable fluid of the present invention was obtained by dropping the hydrogen generating water (c-4) in an amount of a degree to wet the nonwoven fabric into the hydrogen bubble forming body and covering the opening of the hydrogen bubble forming body with the gas-liquid separating portion (fig. 1).

Next, a plastic bottle for carbonated beverages (about 530cc volume when filled to the mouth) was filled with about 515cc of purified water (activated carbon-treated water obtained by treating tap water from japan tenze city with an activated carbon column), and then a device for selectively adding hydrogen to the bioapplication solution was installed in the purified water in the plastic bottle.

After the bottle was laid down and left to stand for 10 minutes, one of the inventors (japanese male in thirty years old with average physique) held the middle abdomen of the plastic bottle in a handful and oscillated 120 times in a rhythm of 2 times/second by moving the wrist left and right to draw a semicircular arc on the wrist so that the cap is opened (total 60 seconds).

The pH, dissolved hydrogen concentration, calcium (Ca) hardness, and magnesium (Mg) hardness of the content liquid before and after the shaking were measured.

Example 2 (shown in FIG. 3) A hydrogen generating system (d-1) containing 300MG of magnesium metal (MG 100: Kanto metal, K.K.) as a hydrogen generating agent and 1500MG of a hydrogen Ion type cation Exchange Resin (a Resin obtained by heat-drying DIAION Ion Exchange Resin SK1 BH: Mitsubishi chemical Corporation, which is a product of strong acid Ion Exchange Resin H type on the market) was wrapped in a nonwoven fabric (Precise RegularC 5160: Asahi Kasei Co., Ltd.) (d-former 2) and heat-sealed, and then the nonwoven fabric was housed together with a cylindrical hydrogen bubble (d-3) made of an acrylic Resin. The apparatus for selectively adding hydrogen to a living organism applicable fluid of the present invention was obtained by dropping water into the hydrogen bubble forming body in an amount of wetting the nonwoven fabric, inserting the gas-liquid separation section described in fig. 1 into the cylindrical hydrogen bubble forming body, and setting the hydrogen bubble forming body in the middle abdominal section so as to leave no space, and opening the hydrogen gas permeation hole (d-4) in a part of the outer wall of the hydrogen bubble forming body above the gas-liquid separation section.

Next, about 515cc of purified water (activated carbon-treated water obtained by treating tap water from japan tenzis city with an activated carbon column) was filled into a plastic bottle for carbonated beverages (about 530cc volume when filled to the mouth), and while inserting the instrument into the mouth of the plastic bottle, the edge of the hydrogen bubble forming body was hooked to the mouth, and the cap was closed without sinking the instrument into water. At this time, the hydrogen gas permeation hole is located above the water level of the purified water.

After leaving for 10 minutes, one of the inventors (japanese male in thirties with average physique) held the middle abdomen of the plastic bottle in a handful and oscillated 120 times in a rhythm of 2 times/second by moving the wrist left and right to draw a semicircular arc so that the cover is placed above the wrist, to reciprocate 120 times (60 seconds in total).

Example 3A hydrogen generating system containing 300MG of magnesium metal (MG 100: Kanto Metal, K.K.) as a hydrogen generating agent and 900MG of malic acid (DL-malic acid, Hibiscus chemical industries, Ltd.) was wrapped in a nonwoven fabric (Precise Regulara C5160: Asahi Kasei Co., Ltd.) together with a water absorbent paper and heat-sealed. Then, the nonwoven fabric was accommodated in a cylindrical hydrogen bubble forming body made of acrylic resin. The apparatus for selectively adding hydrogen to a living organism applicable fluid of the present invention was obtained by dropping water into the hydrogen bubble forming body in an amount of a wet nonwoven fabric, sequentially inserting the plug made of water-absorbent paper and the gas-liquid separation section described in example 1 into the cylindrical hydrogen bubble forming body, setting the plug and the gas-liquid separation section in the middle abdominal section so as to leave no room, and opening a hydrogen gas permeation hole in a part of the outer wall of the hydrogen bubble forming body above the gas-liquid separation section.

Next, about 515cc of purified water (activated carbon-treated water obtained by treating tap water from japan tenzilla city with an activated carbon column) was filled into a plastic bottle for carbonated beverages (about 530cc volume when filled to the mouth), and while the instrument was inserted into the mouth of the plastic bottle, the edge (side) of the hydrogen bubble forming body was hooked to the mouth, and the cap was closed without sinking the instrument into water. At this time, the hydrogen gas permeation hole is located at a position higher than the water level of the purified water.

Comparative example 1A hydrogen generating system was prepared which contained 300mg of magnesium metal as a hydrogen generating agent and 1500mg of a hydrogen Ion type cation Exchange Resin ("DIAION Ion Exchange Resin SK1 BH: Mitsubishi Chemical Corporation", a commercially available product of the strongly acidic Ion Exchange Resin type H), which was dried by heating.

About 515cc of purified water (activated carbon-treated water obtained by treating tap water from Japan Tanskia city with an activated carbon column) was filled into a plastic bottle for carbonated beverages (about 530cc volume when filled to the mouth), and then a hydrogen generating agent was directly put into the purified water in the plastic bottle.

Reference example 1 the pH, dissolved hydrogen concentration, calcium (Ca) hardness, magnesium (Mg) hardness of the purified water used in the examples and comparative examples were measured.

These contents are described below as table 1.

TABLE 1

Description of the reference numerals

a valve

a-1 umbrella-shaped head

a-2 shaft part

a-3 protrusions

b concave element

b-1 center hole

b-2 fan-shaped holes

b-3 edge

Claims

1. An apparatus for selectively adding hydrogen to a biological application fluid, comprising:

a hydrogen generating system containing, as an essential component, a hydrogen generating agent of a metal or a hydrogenated metal having a higher ionization tendency than hydrogen;

a hydrogen bubble forming body which contains the hydrogen generation system, generates hydrogen gas by a reaction between the hydrogen generation system and hydrogen generation water, and has a gas-liquid separation section including an open-close valve; it is characterized in that the preparation method is characterized in that,

the hydrogen bubble forming body is provided in a closed container for housing a biological application liquid, and the hydrogen gas is sent into the closed container for housing the biological application liquid through the gas-liquid separation section to obtain a hydrogen-containing biological application liquid,

the open-close valve is opened by the gas pressure of hydrogen gas generated inside the hydrogen bubble forming body by the reaction between the hydrogen generating system and the hydrogen generating water, and discharges the hydrogen gas to the closed container as the outside of the hydrogen bubble forming body, but is closed after the gas is discharged.