JP2014058406A - Instrument for nondestructively producing high-concentration hydrogen solution - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an instrument for producing hydrogen-dissolved liquid which does not change constituents of raw water while facilitating the hydrogen generating reaction.SOLUTION: The instrument comprises a hydrogen generating system stored in a separator, the hydrogen generating system comprising: a hydrogen generating agent that reacts with raw water to generate hydrogen; a metal-ion sequestering agent that sequesters metal ions eluted from the hydrogen generating agent; and a pH adjusting agent that inhibits or removes hydroxide ions.

Description

  The present invention relates to an apparatus for producing a non-destructive high concentration hydrogen solution.

  As a method for producing hydrogen water, a method using a household electrolytic hydrogen water generator or a method of bringing a metal piece of metal magnesium as a hydrogen generator into contact with water is known (Japanese Patent Application Laid-Open No. 2007-167696).

JP2007-167696A

  When trying to obtain a hydrogen solution using a hydrogen generating agent, the hydrogen generating agent often changes the properties of the raw water when dissolving hydrogen molecules in the raw water (or raw solution, hereinafter the same). For example, when the hydrogen generating agent is magnesium metal, when hydrogen is generated, magnesium ions are eluted in the raw water according to the following formulas (1) and (2), and the pH is inclined to the alkali side.

[Equation 1]
Mg + 2H ₂ O → Mg (OH) ² ₊ + H ² Formula (1)
Mg (OH) 2 ₊ → Mg ²⁺ + 2OH ⁻ (2)
However, it is basically not desirable to change the composition of raw water that is already naturally or artificially composed before and after the hydrogen generation reaction. Changes in ingredients lead to changing the taste of beverages such as tea and mineral water.

  Of course, if the hydrogen-dissolved solution is used when the hydrogen generation reaction has not progressed so much, the elution of magnesium and the alkalinity of the liquid can be minimized. However, in that case, a hydrogen-dissolved solution having a low dissolved hydrogen concentration must be satisfied.

  Therefore, there is a demand for an apparatus for producing a hydrogen-dissolved liquid that promotes the hydrogen generation reaction but does not change the composition of raw water as much as possible (that is, non-destructive).

  The present invention is a non-destructive method comprising a separator that contains a hydrogen generation system comprising a hydrogen generator such as metal magnesium, a metal ion sequestering agent for sequestering metal ions derived from the hydrogen generator, and a pH adjuster. Use high concentration hydrogen solution production equipment.

  By using such a device to accelerate the hydrogen generation reaction in raw water, magnesium ions (or by-products such as cations eluted from the hydrogen generating agent during hydrogen generation) do not increase, and raw water A highly concentrated or supersaturated hydrogen solution can be obtained without changing the pH. By using such a device, it is possible to easily produce a high-concentration hydrogen beverage without changing the flavor of any beverage regardless of the location such as home, workplace, city, store.

It is a figure which shows the manufacturing instrument which concerns on one embodiment of this invention.

  Embodiments of the present invention will be described below.

  In the present invention, the raw water is a liquid such as water or an aqueous solution that is an object in which hydrogen is dissolved using the present invention. Raw water includes beverages such as drinking water, tea and coffee. A hydrogen solution obtained by dissolving hydrogen in raw water is applied to a living body through inhalation (spraying), drinking, injection, and the like, but is not limited thereto. The working component of the hydrogen solution is hydrogen, and its action is mainly to suppress oxidative stress, but is not limited thereto.

  In the present invention, the hydrogen generator is a substance that generates hydrogen. Substances that generate hydrogen by contact with water, such as metals having a higher ionization tendency than hydrogen and hydrogenated compounds containing hydrogenated metals, are included in the hydrogen generating agent. In consideration of good reactivity with water, metallic calcium, calcium hydride, metallic magnesium, magnesium hydride and the like are preferably used. In consideration of the safety of the reaction product, magnesium metal is particularly preferably used.

The sequestering agent of the present invention is an insoluble or hardly soluble substance having a property of adsorbing metal ions inside the isolator, and hardly or hardly dissolves in water, and traps metal ions by dissolving in water. In addition, a substance that generates a substance safe for the living body is included. From the viewpoint of not changing the composition of raw water, an insoluble or hardly soluble sequestering agent such as a cation exchange resin is preferable. Among them, hydrogen containing 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, which releases a hydrogen ion (H ⁺ ) along with the adsorption of a metal ion. An ionic cation exchange resin is more preferred because it also serves as a pH adjuster.

The pH adjuster of the present invention supplies hydroxide ions (H ⁺ ) by supplying hydrogen ions (H ⁺ ) such as citric acid, adipic acid, malic acid, acetic acid, succinic acid, gluconic acid, lactic acid, phosphoric acid, hydrochloric acid and sulfuric acid. A substance having a property of suppressing (neutralization or prevention of formation) OH ⁻ ) and a substance that removes hydroxide ions by hydrolysis to form an insoluble hydroxide. From the viewpoint that the composition of raw water is difficult to change, a pH adjuster that forms an insoluble hydroxide upon hydrolysis, such as an ore containing aluminum ions, is preferable. Among them, alum such as ammonium aluminum sulfate is more preferable because it is hydrolyzed to produce insoluble aluminum hydroxide and also functions as a sequestering agent (flocculating agent) for magnesium ions and calcium ions.

  As described above, the hydrogen ion type cation exchange resin and alum have a function as a sequestering agent and a function as a pH adjusting agent in one agent. This is preferable because the smaller the number of agents stored in the separator, the more unnecessary it is to worry about elution of extra components. Furthermore, insoluble polymer materials with sequestering ability and pH adjustment ability, such as hydrogen ion type cation exchange resin, are not subject to hydrolysis like alum. It is a particularly preferable substance from the viewpoint of not changing.

  Moreover, in order to suppress deterioration with time of the hydrogen generating agent, it is preferable that the hydration number and moisture content of substances contained in the hydrogen generating system such as a sequestering agent and a pH adjuster are small. That is, in terms of the hydration number, it is desirable to be a trihydrate or less, preferably a dihydrate or less, more preferably a monohydrate or less, particularly preferably an anhydrate or an anhydride. In terms of water content, it is desirable that the water content is 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.

  The separator of the present invention is a container containing a hydrogen generation system such as a hydrogen generator, a sequestering agent, and a pH adjuster. While the isolator permeates the raw water, the substance contained in the hydrogen generation system and the residue resulting from the hydrogen generation are made difficult to permeate. The pore size of the separator is desirably 1000 μm or less, preferably 500 μm or less, more preferably 150 μm or less, and particularly preferably 50 μm or less. The separator includes a non-woven bag-like container, a plastic porous container, and the like. In order to further enhance the isolation effect, it is desirable to isolate the hydrogen generation system isolated in a non-woven bag-like container in a nested manner with a hard porous container or the like.

  In addition, the average particle size of the hydrogen generating agent such as metallic magnesium of the present invention is desirably a particle size that does not penetrate to the outside of the separator and can also increase the activity due to the atomization. That is, the average particle size of the hydrogen generating agent is equal to or larger than the pore size of the separator (if the separator is nested, the average pore size of the separator having the smallest pore size among them is the same). The diameter is not more than 3000 μm, preferably not less than the pore size of the separator, and the average particle size is not more than 1000 μm, more preferably not less than the pore size of the separator, and the average particle size is not more than 500 μm, particularly preferably It is desirable that it is not less than the pore size of the separator and the average particle size is not more than 250 μm.

  In the present invention, the high concentration hydrogen solution includes a hydrogen solution having a dissolved hydrogen concentration of 0.1 ppm or more, preferably 1.0 ppm or more. In the present invention, the supersaturated hydrogen solution includes a dissolved hydrogen concentration equal to or higher than the solubility at room temperature and normal pressure, 1.6 ppm or more, 2.0 ppm or more, 3.0 ppm or more, 4.0 ppm or more, 5.0 ppm or more, The high concentration hydrogen solution of 6.0 ppm or more, 7.0 ppm or more, 8.0 ppm or more, 9.0 ppm or more, 10.0 ppm or more is included.

  For the purpose of increasing the dissolved hydrogen concentration of the hydrogen solution, a nondestructive high-concentration hydrogen solution production tool in which the hydrogen generation system of the present invention is housed in a separator is housed in a sealed container and the sealed container. It is desirable to shake appropriately. FIG. 1 shows a manufacturing tool of this example.

  In this case, the sealed container of the present invention includes a container that has been devised so that the contents of the container are not exposed to the atmosphere. Containers with lids such as plastic bottles with caps and aluminum bottles are included in hermetically sealed containers. It is desirable that the sealed container has a portable form and capacity so that a person can easily hold it in his / her hand. A closed container having a capacity of 2 L or less, preferably 1 L or less, particularly preferably 0.5 L or less is desirable, but not limited thereto.

  A preferable material for the sealed container is a container having low hydrogen permeability. The lower the hydrogen permeability, the less the generated hydrogen escapes out of the container system.

  In the present invention, the hydrogen permeability of the sealed container is 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 ° C. and 1 atm) is 20 The closed container filled with clean water (such as activated carbon treated with Fujisawa city tap water passed through an activated carbon column) is immersed in the hydrogen-dissolved water for 5 hours.

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

  It is desirable that the sealed container has a pressure resistance capable of withstanding an increase in internal pressure due to hydrogen generation. It is desirable that the pressure vessel be capable of withstanding an internal pressure of 0.11 MPa in absolute pressure, preferably 0.4 MPa, more preferably 0.5 MPa, and particularly preferably 0.8 MPa. A plastic bottle for carbonated beverages is preferably used. It is desirable that the sealed container is provided with a mechanism (vent slot) for releasing pressure in the middle of opening the cap so that it can be safely opened.

  In the present invention, shaking refers to bringing the solution in the sealed container into contact with hydrogen in the gas phase by applying a physical impact to the sealed container. The shaking of the present invention includes artificial shaking using a machine as well as natural shaking using a hand. Shaking with a shaker, stirrer, ultrasonic generator, etc. is included in such artificial shaking.

  Examples of typical natural shaking according to the present invention are as follows. In other words, a Japanese male in his thirties with an average physique holds the abdomen of the sealed container well and moves the wrist only, so that the cap draws a semicircular arc above the wrist at a rate of 2 round-trips / second. Shake 120 times.

  The shaking time is preferably within 600 seconds, preferably within 60 seconds, more preferably within 30 seconds, and even more preferably within 10 seconds in consideration of the load on the consumer and convenience.

  In consideration of ease of shaking, even after filling with raw water, the sealed container should be provided with a head space with a capacity of 15% or less, preferably 10% or less, particularly preferably 5% or less of the container capacity. Is desirable.

  By shaking, the dissolved hydrogen concentration of the solution after shaking is preferably increased to 1.1 times or more of the dissolved hydrogen concentration before shaking, preferably 2 times or more, more preferably 3 times or more, and still more preferably in order. It is 4 times or more, 5 times or more, 6 times or more, 7 times or more, 8 times or more, 9 times or more, particularly preferably 10 times or more.

  In addition, it is preferable that the internal pressure of the sealed container before shaking be in the state of atmospheric pressure or higher in order to obtain a higher concentration hydrogen solution such as a supersaturated hydrogen solution of 1.6 ppm or higher. The solubility of hydrogen molecules in a hydrogen solution increases as the internal pressure of the generated hydrogen molecules loaded on the sealed container increases, and over time, exceeds the solubility at normal temperature and normal pressure. The reason why the closed container having a hydrogen generation system is allowed to stand for an appropriate period of time such as 10 minutes or 15 hours in the examples described later is to pressurize the closed container from the inside with the generated hydrogen gas. This is because the dissolution of hydrogen molecules in a hydrogen solution can be further promoted by appropriately shaking under pressure.

  By the way, insoluble polymer substances having sequestering ability and pH adjustment ability such as the above-described hydrogen ion type cation exchange resin are metal generators such as metal magnesium, which have a higher ionization tendency than hydrogen and hydrogenation agents containing metal hydrides. Can be combined to form a lean hydrogen generation system in which the three functions of hydrogen generation, sequestering of metal ions, and pH adjustment are closely linked. Hereinafter, a hydrogen generation system composed of metallic magnesium and a hydrogen ion type cation exchange resin will be described as an example.

Normally, when metal magnesium comes into contact with raw water, hydrogen molecules and magnesium hydroxide are generated according to the above-described formula (1). As the reaction mechanism,
Electrons are emitted from metallic magnesium,
Mg → Mg ²⁺ + 2e ⁻ (3)
When,
Electrons derived from metallic magnesium produce hydrogen molecules and hydroxide ions by reducing water molecules.
2H ₂ O + 2e ⁻ → 2OH ⁻ + H ² Formula (4)
And, electrons derived from magnesium metal produce hydrogen molecules by reducing hydrogen ions,
2H ⁺ + 2e ⁻ → H ² Formula (5)
The elementary reaction is considered.

  Here, when the hydrogen ion type cation exchange resin exists adjacent to the metal magnesium, the magnesium ion released according to the formula (3) is adsorbed to the hydrogen ion type cation exchange resin and the hydrogen ion type cation exchange resin. Hydrogen ions are released from the ion exchange resin. Therefore, the electrons released according to the formula (3) reduce the hydrogen ions in the vicinity in preference to reducing water molecules.

  Thus, in the hydrogen generation system of the present invention, in accordance with formula (5) which is a hydrogen generation reaction that does not generate hydroxide ions, in preference to formula (4) that is a hydrogen generation reaction that generates hydroxide ions. Since hydrogen is generated, there is little change in the pH of raw water. Further, in the system, since magnesium ions and hydroxide ions tend to be constantly reduced, the hydrogen generation reaction, which is the positive reaction of the above formula (1), is easily promoted.

  Here, the hydrogen generating agent, the sequestering agent, and the pH adjusting agent are accommodated in a separator such as a nonwoven fabric or a porous container as shown in FIG. 1, and the agent itself or the residue after the reaction is transferred to raw water. Designed not to be. However, the raw water penetrates the separator and comes into contact with the contents of the separator. Therefore, if the raw water contains a hardness component such as magnesium ions, the sequestering agent inside the isolator captures not only metal ions derived from the hydrogen generator but also metal ions derived from such raw water. It is expected that.

  Contrary to that expectation, however, the sequestering ability in the isolator hardly captures the hardness component originally contained in the raw water. That is, the apparatus for producing a non-destructive high-concentration hydrogen solution using an insoluble polymer substance having a sequestering ability and a pH adjusting ability, such as a hydrogen ion type cation exchange resin, in a hydrogen generation system of the present invention It can be said that the metal ions derived from the hydrogen generator such as magnesium dissolved in the metal are not increased and conversely not reduced.

  The inventors did not fully elucidate the reason, but in such a hydrogen generation system, the hydrogen generator and the sequestering agent are in contact with the nectar in a relatively small space inside the separator (mixed). Therefore, it is conceivable that the metal ions derived from the hydrogen generating agent are captured with a considerably higher priority than the metal ions coming from the outside of the separator.

  In the present invention, the state in which the hardness component of raw water is maintained or not changed is not limited to this, but includes the following states, for example.

  That is, purified water obtained by dechlorination of tap water, having a total hardness (Ca hardness + Mg hardness) of about 55 to 65 ppm (such as purified water obtained by treating Fujisawa city tap water through an activated carbon column). In the mouth air phase of a carbonated beverage plastic bottle filled with about 515 cc of raw water (filled with water up to about 530 cc capacity), the non-destructive high concentration hydrogen solution production apparatus of the present invention is placed in water. Close the cap while keeping it from sinking (see Example 1 below), lay the bottle on its side and let it stand for 10 minutes, then model natural shaking (hold the middle of the PET bottle abdomen, wrist The total hardness of the solution that was performed by reciprocating only left and right so that the cap draws a semicircular arc over the wrist at a rate of 2 reciprocations / second) (total hardness of raw water −25 ppm) to (Total hardness of raw water +25 pm), preferably (total hardness of raw water−15 ppm) to (total hardness of raw water + 15 ppm), particularly preferably (total hardness of raw water−10 ppm) to (total hardness of raw water + 10 ppm). is there.

  In the present invention, the state in which the pH of raw water is maintained or not changed is not limited to this, but refers to the following states, for example.

  That is, raw water which is purified water obtained by dechlorination of tap water and having a pH of about 7.0 to 7.8 (such as purified water obtained by passing Fujisawa city tap water through an activated carbon column), The non-destructive high-concentration hydrogen solution production apparatus of the present invention is not submerged in the mouth air phase of a carbonated beverage plastic bottle filled with about 515 cc (about 530 cc capacity when filled with water up to the mouth). Close the cap (see Example 1 below), lay the bottle on its side and let it stand for 10 minutes, then hold the model natural shaking (hold the middle of the PET bottle mid-handed and move only the wrist left and right The pH of the solution obtained by performing a reciprocal movement at a pace of 2 reciprocations / second so that the cap draws a semicircular arc above the wrist by moving to (raw water pH-1.5) to (raw water) pH + 1.5), preferably (pH of raw water−1.0) ~ (PH of the raw water + 1.0), particularly preferably such a state that within the range of (pH-0.5 ppm in the raw water) ~ (pH of the raw water + 0.5).

  Examples of the present invention will be described below. Unless otherwise specified in the present application, various meters used for measuring various physical property values are pH meters (including thermometers) manufactured by HORIBA, Ltd. 13 ”, the model of the same probe“ 9620-10D ”), and the DH meter (dissolved hydrogen meter) is a DH meter (main body model“ DHDI-1 ”, the same electrode (probe) model, HE-5321 ”, repeater model“ DHM-F2 ”).

  The calcium hardness and magnesium hardness were measured by a calmagite colorimetric method using a water quality analyzer “DR / 4000” (manufactured by HACH).

[Examples 1-8, Comparative Examples 1-3, Reference Examples 1-2]
A commercially available strong acid ion exchange resin H type product (DIAION Ion Exchange Resin SK1BH: Mitsubishi Chemical Corporation) was dried by heating to obtain a granular hydrogen ion type cation exchange resin (particle size: about 425 μm to about 1180 μm). . As shown in FIG. 1, a hydrogen generation system, which is a mixture obtained by uniformly dispersing and mixing 30 mg of the obtained hydrogen ion type cation exchange resin and 300 mg of metal magnesium powder (MG100: Kanto Metal Co., Ltd.), The film was wrapped in a non-woven fabric (Precise Regular C5160: Asahi Kasei Co., Ltd.) and heat-sealed, and accommodated in a cylindrical porous container (bottom: circle with a diameter of about 14 mm, height: about 58 mm). After filling 515 cc of purified water (activated carbon treated with Fujisawa city tap water through an activated carbon column) into a carbonated plastic bottle (filled with water up to about 530 cc capacity), the porous container is filled with a porous container While being inserted into the container, an edge (edge) surrounding the ceiling of the porous container was hooked on the mouth, and the cap was closed so that the porous container did not sink into water. The weight ratio of metal magnesium and hydrogen ion type cation exchange resin contained in the obtained hydrogen generator is 1: 0.1.

  The bottle was then laid down and left for 10 minutes with the perforated container in full contact with the raw water, and one of the inventors (a male in his 30s with an average physique) took advantage of the middle of the plastic bottle. The cap was reciprocated 120 times at a rate of 2 reciprocations / second (total 60 seconds) so that the cap would draw a semicircular arc above the wrist by moving only the wrist left and right.

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

  Moreover, after preparing the mixture (Examples 2-8 and Comparative Example 1) which changed content of hydrogen ion type cation exchange resin, and processing it in the same procedure as Example 1, pH of a content liquid, dissolution Hydrogen concentration, calcium (Ca) hardness, and magnesium (Mg) hardness were measured.

  Further, as a comparative example, a plurality of mixtures (comparative examples 2 to 3) containing malic acid (DL-malic acid: Fuso Chemical Industry Co., Ltd.) instead of the hydrogen ion type cation exchange resin were prepared. After processing in the same procedure, the pH, dissolved hydrogen concentration, calcium (Ca) hardness, and magnesium (Mg) hardness of the content solution were measured.

  As Reference Example 1, the pH of purified water, the dissolved hydrogen concentration, calcium (Ca) hardness, and magnesium (Mg) hardness were measured.

  In addition, as Reference Example 2, the hydrogen generation system described in Example 7 was directly separated from the nonwoven fabric and the porous container without being separated by a non-woven fabric and a porous bottle of carbonated beverage filled with about 515 cc of purified water (about 530 cc with full water filling to the mouth). Volume) and left for 10 minutes with the bottle lying down sideways, then the pH, dissolved hydrogen concentration, calcium (Ca) hardness, magnesium (Mg) of the content solution shaken by the method described in Example 1 Hardness was measured.

  These are described below as Table 1.

本発明の非破壊的高濃度水素溶液の製造器具においては、金属マグネシウムの重量が一定であり、水素イオン型陽イオン交換樹脂が金属マグネシウムに対して重量比で０．１〜７の範囲で含有されるとき、原水の溶存水素濃度は、水素イオン型陽イオン交換樹脂の含有量に比例して上昇する。またそのときの原水の硬度（Ｃａ硬度とＭｇ硬度）とｐＨは変わらない。

In the nondestructive high concentration hydrogen solution production apparatus of the present invention, the weight of metal magnesium is constant, and the hydrogen ion type cation exchange resin is contained in the range of 0.1 to 7 by weight with respect to metal magnesium. When this is done, the dissolved hydrogen concentration of the raw water increases in proportion to the content of the hydrogen ion type cation exchange resin. Moreover, the hardness (Ca hardness and Mg hardness) and pH of raw water at that time are not changed.

  Even when the hydrogen ion type cation exchange resin is contained in a weight ratio of 30, the dissolved hydrogen concentration does not increase further, but the hardness of raw water (Ca hardness and Mg hardness) and pH are almost the same. Absent. In other words, in the hydrogen solution using the nondestructive high-concentration hydrogen solution production apparatus of the present invention, a certain buffering action that keeps the pH and hardness of the raw water within a certain range works.

  On the other hand, in Reference Example 2 containing metal magnesium and hydrogen ion type cation exchange resin in a weight ratio of 1: 7, but not directly contained in the separator, this buffering action is Not working at all.

  Therefore, in the present invention, it is important to accommodate the hydrogen generation system in the separator. In addition, the hydrogen generation system has a metal ion sequestering ability such as a hydrogen ion type cation exchange resin when the content of a hydrogen generator containing metal or metal hydride having a higher ionization tendency than hydrogen, such as metal magnesium, is 1. It is desirable that the insoluble polymer substance having pH adjusting ability is contained in a weight ratio of 0.1 or more, preferably 0.5 or more, more preferably 1 or more, particularly preferably 5 or more.

[Examples 9 to 10, Comparative Example 4, Reference Example 3]
A commercially available strong acid ion exchange resin H type product (DIAION Ion Exchange Resin SK1BH: Mitsubishi Chemical Corporation) was dried by heating to obtain a granular hydrogen ion type cation exchange resin (particle size: about 425 μm to about 1180 μm). . As shown in FIG. 1, a hydrogen generation system which is a mixture obtained by uniformly dispersing and mixing 300 mg of the obtained hydrogen ion type cation exchange resin and 300 mg of metal magnesium powder (MG100: Kanto Metal Co., Ltd.) The film was wrapped in a non-woven fabric (Precise Regular C5160: Asahi Kasei Co., Ltd.) and heat-sealed, and accommodated in a cylindrical porous container (bottom: circle with a diameter of about 14 mm, height: about 58 mm). After filling 515 cc of purified water (activated carbon treated with Fujisawa city tap water through an activated carbon column) into a carbonated plastic bottle (filled with water up to about 530 cc capacity), the porous container is filled with a porous container While being inserted into the container, an edge (edge) surrounding the ceiling of the porous container was hooked on the mouth, and the cap was closed so that the porous container did not sink into water. The weight ratio of metal magnesium and hydrogen ion type cation exchange resin contained in the obtained hydrogen generator is 1: 1.

  Thereafter, the bottle was laid down and left for 15 hours so that the porous container was completely in contact with the raw water, and then the pH, dissolved hydrogen concentration, calcium (Ca) hardness, and magnesium (Mg) hardness of the contents were measured.

  In addition, as Example 10, a mixture in which the content of the hydrogen ion type cation exchange resin was 2100 mg (weight ratio of metal magnesium and hydrogen ion type cation exchange resin was 1: 7) was prepared, and the same procedure as in Example 9 was made. Then, the pH, dissolved hydrogen concentration, calcium (Ca) hardness, and magnesium (Mg) hardness of the content liquid were measured.

  Further, as Comparative Example 4, a mixture in which the content of the hydrogen ion type cation exchange resin was 0 mg (the weight ratio of the magnesium metal to the hydrogen ion type cation exchange resin was 1: 0) was prepared. Then, the pH, dissolved hydrogen concentration, calcium (Ca) hardness, and magnesium (Mg) hardness of the content liquid were measured.

  As Reference Example 3, the pH of the purified water, the dissolved hydrogen concentration, the calcium (Ca) hardness, and the magnesium (Mg) hardness were measured.

  These are described in Table 2 below.

表２に記載されるように、本願の水素発生系を隔離体に収容してなる非破壊的高濃度水素溶液の製造器具を用いることで、原水のｐＨと硬度を維持したまま、溶存水素濃度を特異的に高めた高濃度水素溶存液が得られる。

As shown in Table 2, the concentration of dissolved hydrogen is maintained while maintaining the pH and hardness of the raw water by using a non-destructive high concentration hydrogen solution production tool in which the hydrogen generation system of the present application is housed in a separator. A high-concentration hydrogen-dissolved solution with a specific increase can be obtained.

[Examples 11 to 13, Reference Examples 3 to 4]
As shown in FIG. 1, a hydrogen generation system, which is a mixture obtained by uniformly dispersing and mixing 100 mg of alum (baked alum: Fuji Foods Co., Ltd.) and 100 mg of metal magnesium powder (MG100: Kanto Metal Co., Ltd.) The film was wrapped in a non-woven fabric (Precise Regular C5160: Asahi Kasei Co., Ltd.) and heat-sealed, and accommodated in a cylindrical porous container (bottom: circle with a diameter of about 14 mm, height: about 58 mm). After filling 515 cc of purified water (activated carbon treated with Fujisawa city tap water through an activated carbon column) into a carbonated plastic bottle (filled with water up to about 530 cc capacity), the porous container is filled with a porous container While being inserted into the container, an edge (edge) surrounding the ceiling of the porous container was hooked on the mouth, and the cap was closed so that the porous container did not sink into water. The weight ratio of metallic magnesium and alum contained in the obtained hydrogen generating agent is 1: 1.

  The bottle was then laid down and left for 10 minutes with the perforated container in full contact with the raw water, and one of the inventors (a male in his 30s with an average physique) took advantage of the middle of the plastic bottle. The cap was reciprocated 120 times at a rate of 2 reciprocations / second (total 60 seconds) so that the cap would draw a semicircular arc above the wrist by moving only the wrist left and right.

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

  In addition, a plurality of mixtures (Examples 12 to 13) with different alum contents were prepared and treated in the same procedure as in Example 11, and then the pH of the liquid contents, dissolved hydrogen concentration, calcium (Ca) hardness, magnesium (Mg) hardness was measured.

  As Reference Example 4, the pH of purified water, the dissolved hydrogen concentration, calcium (Ca) hardness, and magnesium (Mg) hardness were measured.

  Further, as Reference Example 5, the hydrogen generation system described in Example 12 was directly filled with about 515 cc of purified water without being separated by a nonwoven fabric and a porous container (about 530 cc when filled with water up to the mouth). Volume), left for 10 minutes with the bottle lying down, and then shaken by the method described in Example 11, pH, dissolved hydrogen concentration, calcium (Ca) hardness, magnesium (Mg) Hardness was measured.

  These are described in Table 3 below.

［実施例１４，参考例６］
市販の弱酸性イオン交換樹脂Ｈタイプ品（DIAION Ion Exchange Resin WK40L：Mitsubishi Chemical Corporation）を温熱乾燥することで顆粒状の水素イオン型陽イオン交換樹脂を得た。得られた水素イオン型陽イオン交換樹脂４０００ｍｇと金属マグネシウム粉（ＭＧ１００：株式会社関東金属）３００ｍｇを均等に分散し混合することにより得た混合物である水素発生系を、図１に示すように、不織布（プレシゼRegular C5160：旭化成株式会社）に包み込みヒートシールするとともに、筒状の多孔容器（底部：直径約１４ミリの円、高さ：約５８ミリ）に収容した。炭酸飲料用ペットボトル（口部までの満水充填で約５３０ｃｃ容量）に浄水（藤沢市水道水を活性炭カラムに通して処理した活性炭処理水）を約５１５ｃｃ充填した後、多孔容器をペットボトル口部に挿入しながら、多孔容器天井部を取り囲む縁（へり）を口部に引掛け、多孔容器が水中に沈まないようにしてキャップを閉めた。得られた水素発生剤に含まれる、金属マグネシウムと水素イオン型陽イオン交換樹脂の重量比は約１：１３．３である。

[Example 14, Reference Example 6]
A commercially available weak acidic ion exchange resin H type product (DIAION Ion Exchange Resin WK40L: Mitsubishi Chemical Corporation) was dried by heating to obtain a granular hydrogen ion type cation exchange resin. As shown in FIG. 1, a hydrogen generation system that is a mixture obtained by uniformly dispersing and mixing 4000 mg of the obtained hydrogen ion type cation exchange resin and 300 mg of metal magnesium powder (MG100: Kanto Metal Co., Ltd.) The film was wrapped in a non-woven fabric (Precise Regular C5160: Asahi Kasei Co., Ltd.) and heat-sealed, and accommodated in a cylindrical porous container (bottom: circle with a diameter of about 14 mm, height: about 58 mm). After filling 515 cc of purified water (activated carbon treated with Fujisawa city tap water through an activated carbon column) into a carbonated plastic bottle (filled with water up to about 530 cc capacity), the porous container is filled with a porous container While being inserted into the container, an edge (edge) surrounding the ceiling of the porous container was hooked on the mouth, and the cap was closed so that the porous container did not sink into water. The weight ratio of metal magnesium and hydrogen ion type cation exchange resin contained in the obtained hydrogen generator is about 1: 13.3.

  The bottle was then laid down and left for 10 minutes with the perforated container in full contact with the raw water, and one of the inventors (a male in his 30s with an average physique) took advantage of the middle of the plastic bottle. The cap was reciprocated 120 times at a rate of 2 reciprocations / second (total 60 seconds) so that the cap would draw a semicircular arc above the wrist by moving only the wrist left and right.

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

  As Reference Example 6, the pH of purified water, the dissolved hydrogen concentration, calcium (Ca) hardness, and magnesium (Mg) hardness were measured.

  Hereinafter, these are described in Table 4.

なお、先に記した、原水の「水素発生の際に水素発生剤より溶出する陽イオンなど副生成物」を維持した、または変えない状態とは、これに限るものではないが、たとえば以下のような状態を指す。

It should be noted that the state of maintaining or not changing the “by-products such as cations eluted from the hydrogen generating agent during hydrogen generation” as described above is not limited to this. It refers to such a state.

  The corresponding cation of the high-concentration hydrogen solution (for example, all iron when the device of the present invention uses iron as a hydrogen generator) is (the corresponding cation (mg / L) of raw water -4.5 mg / L). ) To (corresponding cation of raw water (mg / L) +4.5 mg / L), preferably (corresponding cation of raw water (mg / L) -3 mg / L) to (corresponding cation of raw water (mg / L)) +3 mg / L), more preferably (corresponding cation of raw water (mg / L) -2 mg / L) to (corresponding cation of raw water (mg / L) +2 mg / L), more preferably (corresponding cation of raw water) Ions (mg / L) -1 mg / L) to (corresponding cation of raw water (mg / L) +1 mg / L), particularly preferably (corresponding cation of raw water (mg / L) -0.5 mg / L) to (The corresponding cation of raw water (mg / L) + 0.5 mg / L) And that the state, and the like.

[Examples 15 to 19, Comparative Example 5, Reference Example 7]
A commercially available strong acid ion exchange resin H type product (DIAION Ion Exchange Resin SK1BH: Mitsubishi Chemical Corporation) was dried by heating to obtain a granular hydrogen ion type cation exchange resin (particle size: about 425 μm to about 1180 μm). . As shown in FIG. 1, a hydrogen generation system that is a mixture obtained by uniformly dispersing and mixing 1200 mg of the obtained hydrogen ion type cation exchange resin and 600 mg of reduced iron (manufactured by Wako Pure Chemical Industries, Ltd.) as shown in FIG. It was wrapped in (Tyvek 1073B: Asahi DuPont Flash Spun Products Co., Ltd.) and heat-sealed, and housed in a cylindrical porous container (bottom: circle with a diameter of about 14 mm, height: about 58 mm). After filling the bottle of carbonated beverage (full capacity up to about 530cc capacity to the mouth) with Fujisawa city tap water, insert the perforated container into the mouth of the plastic bottle and surround the perimeter of the perforated container (edge) Was put on the mouth, and the cap was closed so that the porous container did not sink into water. The weight ratio of the reduced iron and the hydrogen ion type cation exchange resin contained in the obtained hydrogen generator is 1: 2.

  After that, the bottle was laid down and left for 8 hours so that the porous container was completely in contact with the raw water, and one of the inventors (a male in his 30s with an average physique) took advantage of the middle of the plastic bottle. The cap was reciprocated 120 times at a rate of 2 reciprocations / second (total 60 seconds) so that the cap would draw a semicircular arc above the wrist by moving only the wrist left and right.

  Thereafter, the pH of the content liquid, the dissolved hydrogen concentration, and the total iron were measured to confirm the taste and odor.

  Total iron was measured by the FerroVer method using a water quality analyzer “DR / 4000” (manufactured by HACH) (hereinafter the same).

  Moreover, after preparing multiple (Examples 16-19) the mixture which changed content of reduced iron, and processing in the same procedure as Example 15, pH of a content liquid, dissolved hydrogen concentration, and total iron are measured, The taste and smell were confirmed.

  Moreover, as Comparative Example 5, a mixture containing malic acid (DL-malic acid: Fuso Chemical Industry Co., Ltd.) was used instead of the hydrogen ion type cation exchange resin, and the mixture was treated in the same procedure as in Example 15, The pH of the content liquid, the dissolved hydrogen concentration, and the total iron were measured.

  Further, as Reference Example 7, Fujisawa city tap water pH and total iron were measured.

  Hereinafter, these are described in Table 5.

Claims (8)

A hydrogen generating agent that reacts with raw water to generate hydrogen;
A metal ion sequestering agent that sequesters metal ions eluted from the hydrogen generator;
A device for producing a non-destructive high-concentration hydrogen solution comprising a separator that contains a hydrogen generation system containing a pH adjuster that suppresses or removes hydroxide ions. The device for producing a non-destructive high concentration hydrogen solution according to claim 1,
The said hydrogen generating agent contains metallic magnesium, The manufacturing instrument of the nondestructive high concentration hydrogen solution characterized by the above-mentioned. The apparatus for producing a non-destructive high concentration hydrogen solution according to claim 1 or 2,
The said sequestering agent and the said pH adjuster are one agent which has sequestering ability and pH control ability, The manufacturing instrument of the nondestructive high concentration hydrogen solution characterized by the above-mentioned. In the non-destructive high concentration hydrogen solution production apparatus according to any one of claims 1 to 3,
The agent for sequestering metal ions and adjusting pH is a hydrogen ion type cation exchange resin, a device for producing a non-destructive high concentration hydrogen solution. A hydrogen generating agent that reacts with raw water to generate hydrogen;
A metal ion sequestering agent that sequesters metal ions eluted from the hydrogen generator;
A step of reacting an apparatus for producing a non-destructive high-concentration hydrogen solution containing a hydrogen generating system containing a pH adjuster for suppressing or removing hydroxide ions in a separator with raw water in a sealed container; ,
Non-destructive, having a step of shaking when the sealed container is at an internal pressure higher than atmospheric pressure, and making the dissolved hydrogen concentration of the raw water in the sealed container after shaking double or more compared to the dissolved hydrogen concentration before shaking For producing a highly concentrated hydrogen solution. In the manufacturing method of the non-destructive high concentration hydrogen solution according to claim 5,
The method for producing a nondestructive high-concentration hydrogen solution, wherein the hydrogen generator contains metallic magnesium. In the manufacturing method of the non-destructive high concentration hydrogen solution of Claim 5 or 6,
The method for producing a non-destructive high-concentration hydrogen solution, wherein the sequestering agent and the pH adjusting agent are one agent having sequestering ability and pH regulating ability. The method for producing a non-destructive high concentration hydrogen solution according to any one of claims 5 to 7,
The method for producing a non-destructive high-concentration hydrogen solution, wherein the one agent having a sequestering ability and a pH adjusting ability is a hydrogen ion type cation exchange resin.

Images