JP7075176B2 - A method for suppressing a decrease in the hydrogen content of a hydrogen-containing liquid, a method for suppressing a decrease in the hydrogen content of the hydrogen-containing liquid, and a method for producing a hydrogen-containing liquid. - Google Patents

Description

The present invention relates to an agent for suppressing a decrease in the hydrogen content of a hydrogen-containing liquid, a method for suppressing a decrease in the hydrogen content of a hydrogen-containing liquid, and a method for producing a hydrogen-containing liquid, and in particular, a predetermined metal cation is used as a liquid solvent. A hydrogen content reduction inhibitor and a hydrogen-containing liquid that can suppress a decrease in hydrogen content for a long period of time when hydrogen is dissolved and / or dispersed in a liquid solvent by dissolving it in a predetermined concentration. The present invention relates to a method for suppressing a decrease in hydrogen content and a method for producing a hydrogen-containing liquid.

Soft drink products in Japan are steadily diversifying in response to changes in lifestyle and tastes for eating and drinking.
In addition, due to the growing health consciousness in recent years, it has not only depleting beverages such as mineral water and sugar-free tea-based beverages and palatable beverages such as coffee beverages, but also physiologically active functions for the body. High attention is also being paid to foods for specified health use (so-called Tokuho) and beverages that are subject to foods with functional claims.

In general, polyphenols such as tea catechin, coffee chlorogenic acid, and fruit-derived anthocyanins such as blueberries, citric acid, essential amino acids, dietary fiber, and minerals have a positive effect on the body. Consumers are already aware that it can be given.
Beverages containing these ingredients are introduced to consumers via various media such as televisions and magazines, even if they do not fall under the above-mentioned foods for specified health use or foods with functional claims. This is one motivation for consumers to choose beverage products containing these ingredients.

Among the various solute components contained in the drinking liquid, the solute component that has a positive effect on the body may be a gas component as well as a solid or liquid substance.
For example, the blood circulation promoting effect of carbon dioxide of carbonated water, the fatigue recovery effect of oxygen, and the like are already known.
In addition to the above, hydrogen as a gas solute has been attracting attention in recent years, and soft drinks containing hydrogen, so-called hydrogen water, have already been put on the market, and the types of products are increasing.

The hydrogen water is one in which hydrogen is dissolved and / or dispersed in water, and it is expected that hydrogen will be effective not only for recovery from fatigue but also for stress-related diseases by removing active oxygen in the body. ing.
However, at the present time, the specific behavior of hydrogen in the body and the mechanism of action on the body when the hydrogen water is drunk are still under study, and the details are unclear.
However, several papers have been published to the effect that the improvement of diseases such as diabetes, diet effect, anti-aging effect, etc. have been confirmed by drinking hydrogen water, and if the mechanism of action is elucidated in the future, it will be further. Demand is expected to increase.

In the hydrogen water, the content of hydrogen contained in the water is the most important factor, and considering that hydrogen acts as an active ingredient, it is desirable that the content is high.
However, hydrogen is sparingly soluble in water, and its saturated dissolution amount is 0.806 mg / 100 mL (about 1.6 mg / L (1.6 ppm)) at 20 ° C and 0.974 mg at 0 ° C (about 1.6 mg / L (1.6 ppm)). Since it is a very light gas with a very small amount of 1.9 mg / L (1.9 ppm)), hydrogen once dissolved tends to escape to the outside in a short time.
Since it is extremely difficult to completely prevent the escape of hydrogen, there is a strong demand for a method of suppressing the decrease in hydrogen concentration as much as possible.

In general, the amount of gas dissolved in a liquid solvent follows Henry's law. That is, since "when a dilute solution containing a volatile solute is in equilibrium with the gas phase, the partial pressure of the solute in the gas phase is proportional to the concentration in the solution", the pressure of the gas in contact with the liquid solvent is increased. This makes it possible to increase the amount of gas solute dissolved.
Utilizing the action of Henry's law, for example, it is not difficult to dissolve hydrogen in water in excess of the saturated dissolution amount under standard atmospheric pressure, and several methods have already been disclosed.
For example, in Patent Document 1, as a method of dissolving hydrogen in water, a method of filling a pressure vessel with hydrogen in a high pressure state and sprinkling water in the pressure vessel in a shower shape to bring hydrogen into contact with water. Is disclosed.
Further, in Patent Document 2 and Patent Document 3, water is partitioned by a gas permeable film and a hydrogen phase pressurized to about 1.2 to 2.0 atm (about 0.12 MPa to 0.20 MPa), and the above is described. A method for dissolving hydrogen in water via a gas permeable membrane is disclosed.
By the method disclosed in Patent Documents 1 to 3, hydrogen can be dissolved in water in excess of the saturated dissolution amount.

However, the inventions according to Patent Documents 1 to 3 are methods for dissolving hydrogen in water under high pressure in a hypersaturated state, and even if hydrogen water is produced by the disclosed method and sealed in a predetermined container. According to the partial pressure of hydrogen gas in the head space in the container, the dissolved hydrogen escapes from the water in a short time.
In addition, when the container is opened under atmospheric pressure, the partial pressure of hydrogen in the atmosphere is very small, so even if hydrogen gas is dissolved at high pressure, hydrogen that is oversaturated in water can be removed from the drinking liquid in a short time. I will get out. Therefore, in either case, the decrease in hydrogen concentration could not be effectively suppressed.

Further, as a method for producing hydrogen water, hydrogen is blown into water at a high pressure of 0.2 MPa <P ≦ 0.4 MP through a hollow fiber membrane, and hydrogen gas is allowed to exist in water in the form of colloid-like bubbles of less than 500 nm. A method has been proposed (Patent Document 4).
Compared with Patent Documents 1 to 3, the method according to Patent Document 4 can produce hydrogen water capable of maintaining a high hydrogen content by floating fine bubbles in water.
However, since hydrogen has the characteristic of being extremely easy to escape, it is important to devise a method for filling hydrogen as shown in Patent Document 4 and to prevent hydrogen from escaping from the container when it is sealed in the container. Specifically, a container form such as an aluminum pouch or an aluminum bottle can has been proposed as a suitable container form.
However, devising a hydrogen filling method and devising a container form for filling hydrogen water are still insufficient to suppress a decrease in the hydrogen content in the hydrogen-containing liquid.

Further, no effective means has been studied so far regarding having the liquid solvent itself containing hydrogen possess a function of suppressing a decrease in hydrogen content.

Japanese Patent No. 36064666 Japanese Patent No. 4551964 Japanese Unexamined Patent Publication No. 2013-169153 Japanese Patent No. 5746411

The present invention relates to an agent for suppressing a decrease in hydrogen content in a hydrogen-containing liquid dissolved and / or dispersed in a liquid solvent such as water, a method for suppressing a decrease in hydrogen content in the hydrogen-containing liquid, and a method for suppressing a decrease in hydrogen content in the hydrogen-containing liquid. It is an object of the present invention to provide a method for producing a hydrogen-containing liquid.

When hydrogen is dissolved and / or dispersed in a liquid solvent, it has been conventionally considered that it is desirable that the hardness (mg / L) of the liquid solvent defined by the following formula is less than 120, that is, so-called soft water.
(formula)
Hardness ≒ calcium concentration x 2.5 + magnesium concentration x 4.1 (units are all (mg / L))
However, the inventor of the present application adjusts the concentration of divalent metal cations to 4.0 mg / 100 mL or more, which is a higher concentration range than that of soft water, in a liquid solvent that dissolves and / or disperses hydrogen. We have found a completely new finding that hydrogen dissolved and / or dispersed in a liquid solvent is difficult to escape to the outside and can suppress a decrease in hydrogen content, and the present invention has been completed.

In this application, the terms "dissolution" and "dispersion" are defined as being distinguished as follows.
In the present application, "dissolution" is defined as a state in which a gas, a liquid, or a solid is mixed with a liquid solvent to form a "uniform liquid phase (single phase)" (Chemical Dictionary No. 7 P1468 stock). Published by the company Tokyo Kagaku Dojin).
On the other hand, in the present application, "dispersion" refers to a state in which a substance system is uniformly suspended as fine particles in another liquid solvent, and in particular, the particle size of the substance system in the liquid solvent is ^{10-5 to} 10-. It refers to the state defined as the state of the system at ⁷ cm (Chemistry Dictionary, 7th print, P1278, published by Tokyo Kagaku Dojin Co., Ltd.). Hereinafter, in the description of the present application, the terms dissolution and dispersion have meanings according to the above definitions.

That is, the invention of the present application is
(1)
An agent for suppressing a decrease in hydrogen concentration in a hydrogen-containing liquid containing a divalent metal cation as an active ingredient.
(2)
A hydrogen concentration decrease inhibitor of 1 hydrogen-containing liquid, wherein the divalent metal cation consists of 1 or 2 or more selected from calcium ion, magnesium ion, and zinc ion.
(3)
An agent for suppressing a decrease in hydrogen concentration in a hydrogen-containing solution of 1 or 2, wherein the divalent metal cation is composed of calcium ions and / or magnesium ions.
(4)
An agent for suppressing a decrease in hydrogen concentration in any of 1 to 3 hydrogen-containing liquids, wherein the divalent metal cation is derived from a metal salt.
(5)
4. An agent for suppressing a decrease in hydrogen concentration in a hydrogen-containing liquid according to 4, wherein the metal salt is a chloride.
(6)
A packaged hydrogen-containing beverage characterized by containing any one of 1 to 5 of a hydrogen concentration decrease inhibitor.
(7)
6. A packaged hydrogen-containing beverage according to 6, wherein the concentration of the divalent metal cation in the beverage liquid is 4.0 mg / 100 mL to 60.0 mg / 100 mL.
(8)
A method for suppressing a decrease in hydrogen concentration of a hydrogen-containing liquid, which comprises a step of dissolving and / or dispersing molecular hydrogen in a liquid solvent containing any one of 1 to 5 of the agent for suppressing decrease in hydrogen concentration.
(9)
The hydrogen concentration of the hydrogen-containing liquid of 8 is characterized by containing the hydrogen concentration decrease inhibitor so that the divalent metal cation concentration is in the range of 4.0 mg / 100 mL to 60.0 mg / 100 mL in the liquid solvent. How to suppress the decrease.
(10)
9. A method for suppressing a decrease in hydrogen concentration in a hydrogen-containing liquid of 9, wherein the agent for suppressing a decrease in hydrogen concentration is contained so that the hardness of the liquid solvent is 120 or more.
(11)
A method for reducing the hydrogen concentration of any of 8 to 10 hydrogen-containing liquids, wherein the liquid solvent is water.
(12)
A method for producing a hydrogen-containing liquid, which comprises a step of dissolving and / dispersing molecular hydrogen in a liquid solvent containing any one of 1 to 5 of a hydrogen concentration decrease inhibitor.
(13)
A method for producing 12 hydrogen-containing liquids, which comprises adjusting the hydrogen content of the hydrogen-containing liquid to 2.0 ppm or more.
(14)
A method for producing a hydrogen-containing liquid of 12 or 13, which comprises a step of enclosing the hydrogen-containing liquid in a predetermined container.
It is composed of each invention of.

INDUSTRIAL APPLICABILITY According to the present invention, a hydrogen-containing solution that suppresses a decrease in hydrogen content and a hydrogen-containing solution that suppresses a decrease in hydrogen content in a hydrogen-containing solution that is dissolved and / or dispersed in a liquid solvent such as water by providing the above configuration. A method for suppressing a decrease in hydrogen content and a method for producing a hydrogen-containing liquid can be provided.

It is a conceptual diagram which shows one Embodiment of the manufacturing method of the hydrogen-containing liquid which concerns on this invention, and shows the method of dispersing hydrogen in a liquid solvent through a gas permeation membrane made of a hollow fiber membrane.

1. 1. Liquid solvent The liquid solvent of the hydrogen-containing liquid in the present embodiment is not particularly limited as long as it contains a divalent metal cation concentration of 4.0 mg / 100 mL to 60.0 mg / 100 mL, and water, fruit juice, and vegetables are used. A liquid solvent suitable for drinking such as juice, coffee extract, tea extract, milk, etc. is assumed.
However, in the present embodiment, in view of the influence of other contained components, the liquid solvent is most preferably water containing no sugar, fat, protein, other plant-extracted components and the like.
Further, it is desirable that the liquid solvent is previously degassed to remove the dissolved gas.

2. 2. Divalent metal cations The divalent metal cations contained in the liquid solvent in the present embodiment are not harmful to the body within the concentration range according to the present invention, or when the liquid solvent is water. However, it is desirable that the taste is not significantly affected.
Divalent metal cations include calcium ion, magnesium ion, zinc ion, iron (divalent) ion, nickel (divalent) ion, copper (divalent) ion and the like. In view of the provision, it is desirable to select from calcium ion, magnesium ion, and zinc ion, which have a relatively large intake allowance, and in the present embodiment, calcium ion and magnesium ion are most desirable.
In addition, as a method for adjusting the concentration of these divalent metal cations, when the liquid solvent is water, it is adjusted by mixing a plurality of types of mineral water having known hardness, or for water deionized by ion exchange or the like. Alternatively, a method of adding a metal salt for adjustment and a method of combining these may be selected.
Examples of the metal salt added to the liquid solvent include, for example, calcium ions and food additives such as calcium chloride, calcium lactate, and calcium gluconate.
When adjusting the divalent metal cation concentration by adding a metal salt, deionized water that has been deionized in advance using an ion exchange membrane or the like can also be used.

The concentration of divalent metal cations in the liquid solvent is 4.0 mg / 100 mL to 60.0 mg / 100 mL, more preferably 4.0 mg / 100 mL to 55 mg / mL, 10.0 mg / 100 mL to 55.0 mg / 100 mL. Is more preferable, and 18.0 mg / 100 mL to 55.0 mg / L is the most desirable.
When the divalent metal cation concentration is in the above range, the effect of suppressing the decrease in hydrogen content becomes more remarkable.
In addition, the hardness conversion (hardness (mg / L) ≒ calcium (ion) concentration (mg / L) x 2.5 + magnesium (ion) concentration (mg / L) x 4.1 calculated value) is 120 or more. It is preferably 120 to 1500 mg / L, more preferably 300 to 1470 mg / L, and most preferably 485 to 1470 mg / L. Similar to the divalent metal cation concentration, by setting this numerical value range, the effect of suppressing the decrease in hydrogen content becomes more remarkable.
(Measurement method of divalent metal cation)
For the amount of each mineral in the liquid solvent, an analysis method such as atomic absorption spectroscopy, ion chromatograph method, inductively coupled plasma emission spectrometry, etc. can be appropriately selected, but trace amounts of metal elements can be quantified. An atomic absorption method having the advantage of being independent of the morphology of the sample is desirable.

3. 3. Method of Filling Liquid Solvent with Hydrogen In the present embodiment, the method of filling the liquid solvent with hydrogen is not particularly limited.
Therefore, it is possible to select a method such as hypersaturation dissolution under high pressure or blowing hydrogen into a liquid solvent with a microbubble or the like, which is performed in the conventional production of hydrogen water. Therefore, in consideration of ensuring a higher hydrogen concentration immediately after filling, select a method of dispersing hydrogen in a liquid solvent by a method of dispersing hydrogen in a liquid solvent via a gas permeable film made of a hollow thread film. Is desirable.
Hereinafter, the present embodiment will be described by taking the case where the liquid solvent is water as an example.

(Gas permeable membrane)
The gas permeable membrane used in this embodiment is classified as a so-called homogeneous membrane and has been conventionally used for separating gas components.
The gas permeation membrane is a homogeneous membrane having a gas permeation performance of Ar / N ₂ = 2 or more, and the film thickness is preferably 20 to 80 μm in order to maintain the strength against pressure. It is more preferably ~ 80 μm, and even more preferably 40-60 μm.
The material of the gas permeable film can be selected from polyethylene, polymethylpentene, and silicone rubber, but the gas permeable film formed of silicone rubber is the most suitable.
It is desirable that the silicone rubber is made of polydimethylsiloxane.

(Gas permeation performance)
In the present embodiment, it is desirable that the gas permeation performance of the gas permeation film has a gas permeation ratio Ar (argon) / N ₂ (nitrogen) of 2 or more. The gas permeation ratio is calculated by measuring the gas permeation amount of argon and nitrogen when the pressure on the surface in contact with the permeation film is maintained at 1.0 kgf / cm ² , and the ratio thereof is calculated.
(Hydrogen permeation mechanism)
The gas permeable membrane, which is a homogeneous membrane used in the present embodiment, is a form of a non-porous membrane, and does not have micropores as seen in the porous membrane.
Hydrogen permeation
It is realized by a three-step mechanism of (1) dissolution of gas molecules in a hydrogen permeable film, (2) passage of gas molecules in the hydrogen permeable film, and (3) release of gas molecules from the hydrogen permeable film.
In the present embodiment, a gas permeable membrane is arranged so as to partition water and hydrogen in a closed space filled with hydrogen and adjusted to a predetermined pressure. In the arranged gas permeable membrane, hydrogen is dissolved in the gas permeable membrane material by the dissolution mechanism of (1) described above on the surface in contact with the gas side.
Hydrogen dissolved in the gas permeable membrane material moves to the water side through the gaps in the molecular lattice of the gas permeable membrane material in (2), and the molecular release mechanism of (3) described above acts on the surface in contact with water. Then, it is released into water in the form of ultrafine bubbles while maintaining the gas phase state.

(Hollow fiber membrane)
In the present embodiment, the gas permeation membrane is in the form of a hollow fiber membrane from the viewpoint of increasing the contact area of hydrogen to be permeated, simplifying the device configuration, and improving the permeation efficiency. It is desirable to have.
The hollow fiber membrane is a form of utilization of a gas permeable membrane, and refers to a membrane formed in a thin straw-shaped capillary tube. The hollow fiber membrane module composed of a bundle of a large number of the hollow fiber membranes is housed in a sealed state in a housing container made of a synthetic resin of vinyl chloride or a metal such as aluminum.
Generally, the diameter (inner diameter) of each hollow fiber membrane is about several mm to 100 μm, but in the present embodiment, it is formed to be 500 to 100 μm in order to efficiently flow the liquid solvent. It is desirable, and more preferably 300 to 100 μm.
The length of each hollow fiber membrane can be adjusted according to the application, but if it is too long, the pressure for flowing the liquid solvent will increase. It is desirable that the excluded length, the so-called effective length, is formed to be 450 to 100 mm, more preferably 300 to 100 mm, and even more preferably 250 to 120 mm.
The thickness of the hollow fiber membrane is formed to be about 10 μm to 100 μm, but in order to disperse hydrogen at a higher content, it is preferably 20 to 80 μm in the present embodiment, and 30 to 80 μm. Is more desirable, and 40 to 60 μm is even more desirable.

The procedure for dispersing hydrogen in water will be described below with reference to the drawings.
In FIG. 1, 10 is a hollow fiber membrane module made of silicon (hereinafter referred to as a module), 11 is a housing made of a material such as stainless steel or vinyl chloride, 12 is a hydrogen inlet, 13 is a hydrogen outlet, and 14 is. Hollow fiber membrane bundles, 15 indicate hydrogen inside the housing, 16 indicates an inlet for water, and 17 indicates an outlet for water after hydrogen dispersion.
The module 10 is arranged in a hydrogen water production line (not shown).
In water as a liquid solvent, the concentration of divalent metal cations is adjusted in advance to a value that satisfies the requirements of the present invention.
Water is sent from 16 and circulates inside the tube of each hollow fiber membrane of the hollow fiber membrane bundle 14.
The hydrogen 15 filled inside the housing is dissolved in silicone rubber (polydimethylsiloxane), which is a membrane material, from the outer surface of each hollow fiber membrane of the hollow fiber membrane bundle 14, passes through the membrane, and then the hollow fiber membrane is formed. It is released into water from the inner surface in the form of fine bubbles.
A part of hydrogen is dissolved and the other is dispersed in the state of fine bubbles, and water is sent out from the outlet 17 in a state of containing hydrogen.
The housing 11 is provided with a hydrogen inlet 12 and a hydrogen outlet 13, and the hydrogen 15 is refluxed into the housing 11 while maintaining a pressure of 0.2 MPa to 0.4 MPa for each sample.

(Hydrogen pressurization)
In order to transfer hydrogen into water in the form of ultrafine bubbles via a gas permeable membrane such as a hollow fiber membrane, the pressure on the hydrogen side is preferably 0.21 to 0.40 MPa, which is 0. .24 to 0.30 MPa is more preferable, and 0.25 to 0.30 MPa is further preferable.

4. Form of hydrogen-containing liquid When the liquid solvent is water, the hydrogen-containing liquid shall be provided as a packaged hydrogen-containing beverage enclosed in a container in the form conventionally used for providing hydrogen water such as a bottle can and an aluminum pouch. You can also.

5. Hydrogen residual rate The index of the effect of suppressing the decrease in hydrogen concentration is expressed as "residual rate (%)". In the present embodiment, the residual ratio is a percentage of the hydrogen content (ppm) after a predetermined time with respect to the hydrogen content (ppm) immediately after hydrogen filling.
The hydrogen content can be measured with a needle-type hydrogen concentration measuring device or the like.

Hereinafter, examples of the present application will be described according to the above embodiments.
(1) Preparation of liquid solvent In this example, water containing calcium ions and / or magnesium ions was used as the liquid solvent.
Further, as a solvent for the comparative example sample, deionized water from which metal ions were removed by an ion exchange resin was used.
In this example, the divalent metal cation concentration indicates the total concentration of two types of ions, calcium ion and magnesium ion.
When the metal salt is dissolved in deionized water, the ion concentration can be adjusted from the amount of the metal salt to be dissolved and the mol mass of the metal salt.
In this example, calcium chloride and magnesium chloride were used as metal salts, and the concentrations of calcium ions and magnesium ions were calculated based on the amount of the metal salt added and the mol mass. The mol mass of calcium chloride was 110.98 g / mol, of which the mol mass of calcium was 40 g / mol. For magnesium chloride, the mol mass was calculated at 95.21 g / mol, and the molar mass of calcium was calculated at 24 g / mol.
As a comparative example sample, a sample in which sodium chloride and potassium chloride, which are monovalent metal salts, were dissolved in deionized water at a predetermined concentration was also prepared.
The dissolved metal salts are 2.0 × 10 ^-3 mol / L, respectively.
In addition, both the liquid solvent to which the metal salt is added and the deionized water are prepared by degassing the dissolved gas in advance in a negative pressure environment of -0.08 MPa, sterilizing at 126 ° C for 30 seconds, and then cooling to 25 ° C. used.
In this example, the concentration of the divalent metal cation was quantified using an atomic absorption spectrophotometer (model number: AA240FS) manufactured by VARIAN.

(2) Production of Hydrogen Water As a method for containing hydrogen in water, which is a liquid solvent, a method of dispersing hydrogen in a liquid solvent via a gas permeable film made of a hollow thread film was adopted as described above.
As the gas permeable membrane, a hollow fiber membrane module made of silicon (“Nagasep” model: M40-6000 manufactured by Nagayanagi Kogyo Co., Ltd.) housed in the housing was used, and water as the liquid solvent adjusted in (1) above was used. Was flown at a flow rate of 0.8 L, and the hydrogen pressure in the housing was adjusted to 0.22 MPa to 0.23 MPa.

Further, the number of hollow fiber membranes per module of the hollow fiber membrane module of the above specifications used in this embodiment is 6000, and the film thickness is 40 μm. Further, the length (effective length) of the hollow fiber membrane used was in the range of 140 to 440 mm.
The hydrogen content in the hydrogen water was measured using a needle-type hydrogen concentration measuring device manufactured by Unisense.

(Result evaluation method)
The effect of suppressing the decrease in hydrogen content was ◎, 5 to 10% of the effect of 10% or more compared with the one having the lowest residual rate in the comparative example samples in both Example 1 and Example 2. In the case of ○, those less than 5% were regarded as Δ.

[Example 1] Comparison of effect of suppressing decrease in hydrogen content between divalent metal cation and monovalent metal cation In Example 1, Example Samples 1 and 2 and Comparative Example Sample 1 under the following conditions. 2 was adjusted. For the filling of the liquid solvent with hydrogen, the method using the hollow fiber membrane described above was commonly used. For each example sample and comparative example use, the total concentration of calcium ion and magnesium ion is described. As Comparative Example Sample 3, a sample in which hydrogen was dispersed in deionized water by the same method as in Example Sample was prepared.
(Example sample 1)
After dissolving 0.2 × 10 ^-3 mol / 100 mL of calcium chloride in deionized water treated with an ion exchange membrane, hydrogen was dispersed using a hollow fiber membrane module under the above-mentioned conditions.
After the hydrogen content became stable, 2 L was recovered in a stainless beaker and left as it was at room temperature of 15 to 20 ° C. for 3 hours.
(Example sample 2)
After dissolving 0.2 × 10 ^-3 mol / 100 mL of magnesium chloride in deionized water treated with an ion exchange membrane, hydrogen was dispersed using a hollow fiber membrane module under the above-mentioned conditions.
After the hydrogen content became stable, 2 L was recovered in a stainless beaker and left as it was at room temperature of 15 to 20 ° C. for 3 hours.
(Comparative Example Sample 1)
After dissolving 0.2 × 10 ^-3 mol / 100 mL of potassium chloride in deionized water treated with an ion exchange membrane, hydrogen was dispersed using a hollow fiber membrane module under the above-mentioned conditions.
After the hydrogen content became stable, 2 L was recovered in a stainless beaker and left as it was at room temperature of 15 to 20 ° C. for 3 hours.
(Comparative Example Sample 2)
After dissolving 0.2 × 10 ^-3 mol / 100 mL of sodium chloride in deionized water treated with an ion exchange membrane, hydrogen was dispersed using a hollow fiber membrane module under the above-mentioned conditions.
After the hydrogen content became stable, 2 L was recovered in a stainless beaker and left as it was at room temperature of 15 to 20 ° C. for 3 hours.

Table 1 shows changes in calcium ion and magnesium ion concentrations and hydrogen contents in Examples 1 and 2 and Comparative Examples Samples 1 and 2 with time.
The molar concentrations of all metal salts were 2.0 × 10 ^-3 mol / L.

(Discussion)
When the liquid solvent was water containing monovalent metal cations, no significant difference was observed in the change in hydrogen concentration as compared with deionized water, regardless of the ion concentration.
On the other hand, when water containing divalent metal cations was used, the effect of suppressing the decrease in hydrogen content after 3 hours was more remarkable than that of deionized water.

[Example 2] Comparison of effect of suppressing decrease in hydrogen content due to change in ion concentration In Example 2, Examples 3 to 8 were prepared under the following conditions. For the filling of the liquid solvent with hydrogen, the method using the hollow fiber membrane described above was commonly used. For each example sample and comparative example use, the total concentration of calcium ion and magnesium ion is described. As Comparative Example Sample 4, a sample in which hydrogen was dispersed in deionized water by the same method as in Example Sample was prepared.

(Example sample 3)
A hollow fiber membrane module was used to disperse hydrogen in mineral water adjusted to a calcium ion concentration of 8.0 mg / 100 mL and a magnesium ion concentration of 2.6 mg / 100 mL under the above-mentioned conditions.
After the hydrogen content became stable, 2 L was recovered in a stainless beaker and left as it was at room temperature of 15 to 20 ° C. for 3 hours.
(Example sample 4)
Hydrogen was dispersed in mineral water having a calcium ion concentration of 46.8 mg / 100 mL and a magnesium ion concentration of 7.45 mg / 100 mL using a hollow fiber membrane module under the above-mentioned conditions.
After the hydrogen content became stable, 2 L was recovered in a stainless beaker and left as it was at room temperature of 15 to 20 ° C. for 3 hours.
(Example sample 5)
The mineral water used in Example Sample 9 was diluted 2-fold with deionized water, and a hollow fiber membrane module was used under the above-mentioned conditions to disperse hydrogen.
After the hydrogen content became stable, 2 L was recovered in a stainless beaker and left as it was at room temperature of 15 to 20 ° C. for 3 hours.
(Example sample 6)
The mineral water used in Example Sample 9 was diluted 3-fold with deionized water, and a hollow fiber membrane module was used under the above-mentioned conditions to disperse hydrogen.
After the hydrogen content became stable, 2 L was recovered in a stainless beaker and left as it was at room temperature of 15 to 20 ° C. for 3 hours.

Table 2 shows changes in the calcium ion and magnesium ion concentrations and the hydrogen content in the Example Samples 3 to 6 and the Comparative Example Sample 4 with time.

(Discussion)
When the total concentration of calcium ion and magnesium ion was within the range of the present invention, a significant difference was found in the hydrogen residual rate. Although the specific action is unknown, it is considered that the presence of the divalent metal cation inhibits the withdrawal of hydrogen dispersed in water.

In this example, even when Example Samples 1 to 6 are sealed in an aluminum pouch and an aluminum bottle can immediately after hydrogen filling and measured after the same time has elapsed after heat sterilization, they are almost the same. The effect of suppressing the decrease in hydrogen content was observed.

The present invention suppresses a decrease in hydrogen content over a long period of time when hydrogen is dissolved and / or dispersed in a liquid solvent by dissolving a predetermined metal cation in a liquid solvent at a predetermined concentration. It is applicable to a possible method for suppressing a decrease in hydrogen content, a method for suppressing a decrease in hydrogen content of a hydrogen-containing liquid, and a method for producing a hydrogen-containing liquid.

10 Hollow fiber membrane module 11 Housing 12 Hydrogen inlet 13 Hydrogen outlet 14 Hollow fiber membrane bundle 15 Hydrogen 16 Water inlet 17 Water outlet

Claims (3)

A packaged hydrogen-containing beverage containing an agent for suppressing a decrease in the hydrogen concentration of a hydrogen-containing liquid containing a divalent metal cation consisting of 1 or 2 selected from calcium ions and magnesium ions as an active ingredient.
The concentration of the divalent metal cation in the drinking liquid is 10.0 mg / 100 mL to 60.0 mg / 100 mL .
The magnesium ion concentration in the drinking liquid is 2.48 mg / 100 mL or more.
A packaged hydrogen-containing beverage characterized by this. The packaged hydrogen-containing beverage according to claim 1 , wherein the hydrogen content is 2.0 ppm or more. A liquid solvent containing a divalent metal cation consisting of 1 or 2 selected from calcium ions and magnesium ions, wherein the divalent metal cation concentration is 10.0 mg / 100 mL to 60.0 mg / 100 mL . A method for suppressing a decrease in hydrogen concentration in a packaged hydrogen-containing beverage, which comprises dissolving and / or dispersing molecular hydrogen in a liquid solvent having a magnesium ion concentration of 2.48 mg / 100 mL or more .

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