JP2017104842A - Apparatus and method for producing hydrogen-containing liquid - Google Patents

Apparatus and method for producing hydrogen-containing liquid Download PDF

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JP2017104842A
JP2017104842A JP2016095438A JP2016095438A JP2017104842A JP 2017104842 A JP2017104842 A JP 2017104842A JP 2016095438 A JP2016095438 A JP 2016095438A JP 2016095438 A JP2016095438 A JP 2016095438A JP 2017104842 A JP2017104842 A JP 2017104842A
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hydrogen
capsule
containing liquid
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liquid
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JP6340033B2 (en
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亮介 黒川
Ryosuke Kurokawa
亮介 黒川
文武 佐藤
Fumitake Sato
文武 佐藤
文平 佐藤
Bunpei Sato
文平 佐藤
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Miz Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/08Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents with metals
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23FCOFFEE; TEA; THEIR SUBSTITUTES; MANUFACTURE, PREPARATION, OR INFUSION THEREOF
    • A23F3/00Tea; Tea substitutes; Preparations thereof
    • A23F3/06Treating tea before extraction; Preparations produced thereby
    • A23F3/14Tea preparations, e.g. using additives
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23FCOFFEE; TEA; THEIR SUBSTITUTES; MANUFACTURE, PREPARATION, OR INFUSION THEREOF
    • A23F5/00Coffee; Coffee substitutes; Preparations thereof
    • A23F5/10Treating roasted coffee; Preparations produced thereby
    • A23F5/14Treating roasted coffee; Preparations produced thereby using additives, e.g. milk, sugar; Coating, e.g. for preserving
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L2/00Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
    • A23L2/52Adding ingredients
    • A23L2/54Mixing with gases
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/68Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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  • Non-Alcoholic Beverages (AREA)
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  • Mixers With Rotating Receptacles And Mixers With Vibration Mechanisms (AREA)
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Abstract

PROBLEM TO BE SOLVED: To provide an apparatus and method for producing hydrogen-containing liquid that can produce a hydrogen-containing liquid whose hydrogen concentration exceeds 6 ppm after 10 minutes, and exceeds 10 ppm after 24 hours.SOLUTION: Provided is an apparatus for producing hydrogen-containing liquid including: a hydrogen generating agent 11 that reacts with water to generate hydrogen gas; a capsule 20 for containing the hydrogen generating agent and discharging the internally generated hydrogen gas to the outside; and a container 30 for containing a liquid L to be added with the hydrogen gas generated inside the capsule, and in which the ratio (V/W) of the volume (V ml) of the capsule to the weight (Wg) of the hydrogen generating agent is set at 11.4 or less, more preferably 8.2 or less.SELECTED DRAWING: Figure 1

Description

本発明は、水素を含有する液体を生成するための装置及び方法に関する。   The present invention relates to an apparatus and method for producing a hydrogen-containing liquid.

本件出願人は、水と反応することにより水素ガスを発生するアルミニウムなどの水素発生系と、一方向弁を有し水素発生系を収容する水素気泡形成体と、を含む生体適用液への水素添加器具を先に提案した(特許文献1)。   The applicant of the present application provides a hydrogen generation system such as aluminum that generates hydrogen gas by reacting with water, and a hydrogen bubble forming body that has a one-way valve and accommodates the hydrogen generation system. An additive device was previously proposed (Patent Document 1).

特許第4652479号公報Japanese Patent No. 4651479

水素含有液体を生物の体内に取り込むことにより酸化ストレスの抑制などの効能が得られることは、多数の論文等により報告されている。しかしながら、液体を飲用などによって体内に取り込むにしても量的な限界がある。このため、同じ量であっても高濃度水素を含有する液体の生成装置の開発が望まれている。本件出願人は、先に提案した上記従来特許により、10分後の水素濃度が5ppm、24時間後の水素濃度が7ppmの水素含有液体を生成することに成功したが、同様の条件で10分後の水素濃度が6ppm、24時間後の水素濃度が10ppmを超える水素含有液体を生成するには至らなかった。   It has been reported in a number of papers and the like that an effect such as suppression of oxidative stress can be obtained by incorporating a hydrogen-containing liquid into a living body. However, even if the liquid is taken into the body by drinking or the like, there is a quantitative limit. For this reason, development of the production | generation apparatus of the liquid which contains high concentration hydrogen even if it is the same quantity is desired. The present applicant has succeeded in producing a hydrogen-containing liquid having a hydrogen concentration of 10 ppm after 10 minutes and a hydrogen concentration of 7 ppm after 24 hours according to the above-mentioned conventional patent. It was not possible to produce a hydrogen-containing liquid in which the later hydrogen concentration was 6 ppm and the hydrogen concentration after 24 hours exceeded 10 ppm.

本発明が解決しようとする課題は、10分後の水素濃度が6ppm、24時間後の水素濃度が10ppmを超える水素含有液体を生成することができる水素含有液体の生成装置及び方法を提供することである。   The problem to be solved by the present invention is to provide a hydrogen-containing liquid producing apparatus and method capable of producing a hydrogen-containing liquid having a hydrogen concentration after 10 minutes of 6 ppm and a hydrogen concentration after 24 hours exceeding 10 ppm. It is.

本発明は、水分と反応して水素ガスを発生する水素発生剤と、前記水素発生剤が収納され、内部で発生した水素ガスを外部へ排出されるカプセルと、前記カプセルの内部で発生した水素ガスの添加対象たる液体を収納する容器と、を備える水素含有液体の生成装置において、前記水素発生剤の重量(Wg)に対する前記カプセルの容積(Vml)の比率(V/W)を、11.4以下、より好ましくは8.2以下に設定することにより、上記課題を解決する。   The present invention relates to a hydrogen generating agent that reacts with moisture to generate hydrogen gas, a capsule that contains the hydrogen generating agent and discharges the hydrogen gas generated inside, and hydrogen generated inside the capsule. 10. A hydrogen-containing liquid production apparatus comprising: a container that contains a liquid to which gas is to be added; and a ratio (V / W) of a volume (Vml) of the capsule to a weight (Wg) of the hydrogen generating agent. The above-mentioned problem is solved by setting it to 4 or less, more preferably 8.2 or less.

本発明によれば、10分後の水素濃度が6ppm、24時間後の水素濃度が10ppmを超える水素含有液体を生成することができる。   According to the present invention, a hydrogen-containing liquid having a hydrogen concentration after 10 minutes of 6 ppm and a hydrogen concentration after 24 hours exceeding 10 ppm can be produced.

本発明に係る水素含有液体の生成装置の一実施の形態を示す構成部品図である。It is a component diagram which shows one Embodiment of the production | generation apparatus of the hydrogen containing liquid which concerns on this invention. 図1のカプセルを示す斜視図である。It is a perspective view which shows the capsule of FIG. 図2AのIIB-IIB線に沿う断面図である。It is sectional drawing which follows the IIB-IIB line | wire of FIG. 2A. 図2AのIIC-IIC線に沿う断面図である。It is sectional drawing which follows the IIC-IIC line | wire of FIG. 2A. 図2AのIID-IID線に沿う矢視図である。It is an arrow line view which follows the IID-IID line of FIG. 2A. 図1に示す水素含有液体の生成装置の使用方法を示す図である。It is a figure which shows the usage method of the production | generation apparatus of the hydrogen containing liquid shown in FIG. 図1に示す水素含有液体の生成装置の使用方法を示す図である。It is a figure which shows the usage method of the production | generation apparatus of the hydrogen containing liquid shown in FIG. 図1に示す水素含有液体の生成装置の使用方法を示す図である。It is a figure which shows the usage method of the production | generation apparatus of the hydrogen containing liquid shown in FIG. 図1に示す水素含有液体の生成装置の使用方法を示す図である。It is a figure which shows the usage method of the production | generation apparatus of the hydrogen containing liquid shown in FIG. 図1に示す水素含有液体の生成装置の使用方法を示す図である。It is a figure which shows the usage method of the production | generation apparatus of the hydrogen containing liquid shown in FIG. 図1に示す水素含有液体の生成装置の使用方法を示す図である。It is a figure which shows the usage method of the production | generation apparatus of the hydrogen containing liquid shown in FIG. 図1に示す水素含有液体の生成装置の使用方法を示す図である。It is a figure which shows the usage method of the production | generation apparatus of the hydrogen containing liquid shown in FIG. 図1に示す水素含有液体の生成装置の使用方法を示す図である。It is a figure which shows the usage method of the production | generation apparatus of the hydrogen containing liquid shown in FIG. 本発明に係る水素含有液体の生成装置の他の実施の形態を示す構成部品図である。It is a component diagram which shows other embodiment of the production | generation apparatus of the hydrogen containing liquid which concerns on this invention. 図4に示す水素含有液体の生成装置の使用方法を示す図である。It is a figure which shows the usage method of the production | generation apparatus of the hydrogen containing liquid shown in FIG. 本発明に係る水素含有液体の生成装置及び方法を用いて水素含有液体を生成した実施例1,2及び比較例1,2を示すグラフである。It is a graph which shows Example 1, 2 and Comparative Examples 1 and 2 which produced | generated the hydrogen containing liquid using the production | generation apparatus and method of the hydrogen containing liquid which concern on this invention. 本発明に係る水素含有液体の生成装置及び方法を用いて水素含有液体を生成した実施例3,4及び比較例3,4を示すグラフである。It is a graph which shows Example 3, 4 and Comparative Examples 3 and 4 which produced | generated the hydrogen containing liquid using the production | generation apparatus and method of the hydrogen containing liquid which concern on this invention.

以下、本発明に係る水素含有液体の生成装置及び方法の一実施の形態を説明する。本実施形態の生成装置1は、水分と反応して水素ガスを発生する水素発生剤11と、内部で発生した水素ガスは外部へ排出されるが外部からの液体は導入されない一方向弁21(逆止弁又はガス透過膜であってもよい)を有し、前記水素発生剤11を入れるカプセル20と、前記カプセル20の内部で発生した水素ガスの添加対象たる液体Lを入れる容器30と、を備える。   Hereinafter, an embodiment of a hydrogen-containing liquid producing apparatus and method according to the present invention will be described. The generating apparatus 1 of this embodiment includes a hydrogen generating agent 11 that generates hydrogen gas by reacting with moisture, and a one-way valve 21 that discharges hydrogen gas generated inside to the outside but does not introduce liquid from the outside. A capsule 20 containing the hydrogen generating agent 11, a container 30 containing a liquid L to be added with hydrogen gas generated inside the capsule 20, Is provided.

本実施形態における液体Lは、本実施形態の生成装置1を用いて水素分子を溶存させるべき対象たる液体の全てを含む。液体Lは、水または水溶液などのほか、飲料水、茶、コーヒーなどの各種飲料を含む。また、注射・点滴・輸液などの用途に浸透圧調製された生理食塩水、栄養素や電解質補給のために調整された注射溶液、薬剤を溶解した注射溶液、輸血に用いられる輸血製剤(輸血用血液)・自己血液、経腸液、臓器の保存のために調合された臓器保存液などを含む。特に本実施形態における液体Lは、人間を含む動物や植物などの生体に適用することができる液体を含む。そして、この種の液体Lに水素を溶存させ、こうして得られる水素含有液体を、口又は鼻からの吸入又は噴霧、口からの飲用、皮膚又は静脈・動脈への注射などにより各種生体に適用される。水素含有液体、特に過飽和を含む高濃度水素含有液体の作用成分は水素であり、その作用は主として酸化ストレスの抑制である。   The liquid L in the present embodiment includes all of the liquids to be dissolved in the hydrogen molecules using the generation device 1 of the present embodiment. The liquid L includes various drinks such as drinking water, tea, and coffee in addition to water or an aqueous solution. In addition, physiological saline osmotically adjusted for uses such as injection, infusion, and infusion, injection solutions adjusted for nutrient and electrolyte replenishment, injection solutions in which drugs are dissolved, blood transfusion preparations used for blood transfusions (blood for transfusion) ) ・ Includes autologous blood, enteral fluid, organ preservation solution formulated for organ preservation, and the like. In particular, the liquid L in the present embodiment includes a liquid that can be applied to living bodies such as animals and plants including humans. Then, hydrogen is dissolved in this type of liquid L, and the hydrogen-containing liquid thus obtained is applied to various living bodies by inhalation or spraying from the mouth or nose, drinking from the mouth, injection into the skin, veins, or arteries. The The active component of a hydrogen-containing liquid, particularly a high-concentration hydrogen-containing liquid containing supersaturation, is hydrogen, and its action is mainly to suppress oxidative stress.

本実施形態における水素発生剤11は、水分と反応して水素ガスを発生する材料であり、具体的には、水素よりイオン化傾向が大きい金属材料と、この金属材料と水分との反応を促進する反応促進剤とを含む。水素発生剤11を、水が透過する袋体12に入れたものを水素発生体10と称する。金属材料は、水分と反応することで水素を発生させる物質であり、水素よりイオン化傾向が大きい金属単体又は水素化金属を含む水素化化合物などが含まれる。水分との反応性の良さを考慮すると、金属カルシウム、水素化カルシウム、金属マグネシウム、水素化マグネシウムなどは好適に用いられる。反応生成物の安全性などを考慮し、金属マグネシウムは特に好適に用いられる。また、反応生成物の安全性や食品衛生法を考慮すれば、鉄、アルミ、ニッケル、コバルトは好適に用いられる。なかでも、金属アルミニウムは、美観、コスト、及び取り扱い上の安全性の観点からも好適に用いられる。   The hydrogen generating agent 11 in the present embodiment is a material that reacts with moisture to generate hydrogen gas, and specifically, promotes the reaction between a metal material having a higher ionization tendency than hydrogen and the metal material and moisture. And a reaction accelerator. A material in which the hydrogen generating agent 11 is put in a bag 12 through which water passes is referred to as a hydrogen generating member 10. The metal material is a substance that generates hydrogen by reacting with moisture, and includes a metal simple substance having a higher ionization tendency than hydrogen or a hydrogenated compound containing a metal hydride. In consideration of good reactivity with moisture, calcium metal, calcium hydride, magnesium metal, magnesium hydride and the like are preferably used. In consideration of the safety of the reaction product, magnesium metal is particularly preferably used. In consideration of the safety of the reaction product and the food hygiene law, iron, aluminum, nickel, and cobalt are preferably used. Among these, metal aluminum is preferably used from the viewpoint of aesthetics, cost, and safety in handling.

上述した金属材料及び反応促進剤を収納する袋体12は、水が透過する材料からなる。本実施形態の袋体12は、液体Lと金属材料及び反応促進剤とを確実に隔離するために設けられるものであり、不織布などの材料を例示することができる。こうした袋体12は、水素ガスや水は透過するが、金属材料、反応促進剤、その反応残渣を透過させない。こうした袋体12のポアサイズは、1000μm以下、好ましくは500μm以下、より好ましくは150μm以下、特に好ましくは50μm以下である。この袋体12のポアサイズとの関係でいえば、金属材料、反応促進剤の平均粒径は、袋体12の外部へ透過することなく、かつ、微粒子化による活性の増大も期せるような粒径であることが望ましい。たとえば、金属材料の平均粒径は、3000μm以下、好ましくは1000μm以下、さらに好ましくは500μm以下、特に好ましくは250μm以下である。   The bag 12 containing the metal material and the reaction accelerator described above is made of a material that allows water to pass therethrough. The bag body 12 of the present embodiment is provided in order to reliably separate the liquid L from the metal material and the reaction accelerator, and examples thereof include a material such as a nonwoven fabric. Such a bag 12 permeates hydrogen gas and water, but does not permeate metal materials, reaction accelerators, and reaction residues thereof. The pore size of such a bag 12 is 1000 μm or less, preferably 500 μm or less, more preferably 150 μm or less, and particularly preferably 50 μm or less. Regarding the relationship with the pore size of the bag body 12, the average particle diameter of the metal material and the reaction accelerator does not permeate the outside of the bag body 12 and can be expected to increase the activity by micronization. The diameter is desirable. For example, the average particle size of the metal material is 3000 μm or less, preferably 1000 μm or less, more preferably 500 μm or less, and particularly preferably 250 μm or less.

本実施形態の水素発生剤11は、金属材料のほか、必要に応じて、金属イオン封鎖剤やpH調整剤など水素発生反応を促進する反応促進剤を含んでもよい。   In addition to the metal material, the hydrogen generator 11 of the present embodiment may include a reaction accelerator that promotes the hydrogen generation reaction, such as a sequestering agent and a pH adjuster, as necessary.

本実施形態で用いることができる金属イオン封鎖剤としては、水に全くあるいはほとんど溶解せず、カプセル20または袋体12の内部において金属イオンを吸着する性質を有する物質を生成する物質を含む。陽イオン交換樹脂など、不溶性または難溶性の金属イオン封鎖剤は好適に用いられる。なかでも、金属イオンの吸着とともに、水素イオン(H)を放出する、スルホン酸基を交換基とする酸性陽イオン交換樹脂またはカルボン酸基を交換基とする酸性陽イオン交換樹脂を含む、水素イオン型陽イオン交換樹脂は、pH調整剤としての機能も兼ねるため、さらに好ましい。 The sequestering agent that can be used in the present embodiment includes a substance that does not dissolve at all or hardly in water and generates a substance having a property of adsorbing metal ions inside the capsule 20 or the bag body 12. An insoluble or hardly soluble sequestering agent such as a cation exchange resin is preferably used. 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.

本実施形態で用いることができるpH調整剤としては、クエン酸、アジピン酸、リンゴ酸、酢酸、コハク酸、グルコン酸、乳酸、リン酸、塩酸、硫酸など水素イオン(H)を供給することで水酸化物イオン(OH)を抑制(中和または生成防止)する性質を有する物質、及び加水分解を受け不溶性の水酸化物を形成することで水酸化物イオンを除去する物質を含む。アルミニウムイオンを含む鉱石など、加水分解を受け不溶性の水酸化物を形成するpH調整剤は好適に用いられる。なかでも、硫酸アンモニウムアルミニウムなどのミョウバンは、加水分解を受け不溶性の水酸化アルミニウムを生成する一方、マグネシウムイオンやカルシウムイオンに対する金属イオン封鎖剤(凝集剤)としての機能も兼ねるため、さらに好ましい。上述のように、水素イオン型陽イオン交換樹脂やミョウバンは、一剤で金属イオン封鎖剤としての機能とpH調整剤としての機能を兼ねるので、より好ましい物質である。 As a pH adjusting agent that can be used in the present embodiment, 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 are supplied. And a substance having a property of suppressing (neutralizing or preventing generation) hydroxide ions (OH ), and a substance that removes hydroxide ions by hydrolysis to form insoluble hydroxides. A pH adjuster that undergoes hydrolysis to form an insoluble hydroxide, such as an ore containing aluminum ions, is preferably used. 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, hydrogen ion type cation exchange resin and alum are more preferable substances because they serve as a metal ion sequestering agent and a pH adjusting agent.

さらに、金属材料の水素発生反応を促進する水素発生反応促進剤として、酸またはアルカリ剤などを用いることができる。酸としては、これに限るものではないが、反応後に固形の沈殿物を生じる酸、またはイオン交換樹脂などの固形酸などが好適に用いられる。また、アルミニウムや亜鉛などの両性金属を水素発生剤として用いる場合は、酸の他、水酸化カルシウム、酸化カルシウム、陰イオン交換樹脂などアルカリ剤を用いることもできる。なかでも、水酸化カルシウム(消石灰)、生石灰(酸化カルシウム)、焼成カルシウム、酸化マグネシウム、水酸化マグネシウム、陰イオン交換樹脂など食品添加物であるアルカリ剤は好適に用いられる。アルミニウムなどの食品添加物である水素よりイオン化傾向の大きい金属と反応して沈殿物を生じる水素発生反応促進剤は、該金属の金属イオンの水素発生反応後の再溶出を抑制するため、生体に適用される液体Lの特性を実質的に変えない。   Furthermore, an acid or an alkali agent can be used as a hydrogen generation reaction accelerator that accelerates the hydrogen generation reaction of the metal material. Although it does not restrict to this as an acid, The acid which produces | generates a solid precipitate after reaction, or solid acids, such as an ion exchange resin, are used suitably. When an amphoteric metal such as aluminum or zinc is used as a hydrogen generator, an alkali agent such as calcium hydroxide, calcium oxide, or anion exchange resin can be used in addition to an acid. Among these, alkaline agents that are food additives such as calcium hydroxide (slaked lime), quick lime (calcium oxide), calcined calcium, magnesium oxide, magnesium hydroxide, anion exchange resin are preferably used. The hydrogen generation reaction accelerator that forms a precipitate by reacting with a metal that has a higher ionization tendency than hydrogen, which is a food additive such as aluminum, suppresses re-elution of the metal ion of the metal after the hydrogen generation reaction. It does not substantially change the properties of the applied liquid L.

なお、金属材料の経時劣化を抑制するために、金属イオン封鎖剤やpH調整剤など水素発生系に含まれる物質の水和数や含水率は少ない方が好ましい。すなわち、水和数でいうと、3水和物以下、好ましくは2水和物以下、より好ましくは1水和物以下、特に好ましくは無水和物や無水物であることが望ましい。含水率でいうと、含水率40重量%以下、好ましくは30重量%以下、より好ましくは20重量%以下、特に好ましくは15重量%以下であることが望ましい。   In order to suppress deterioration over time of the metal material, it is preferable that the hydration number and water content of substances contained in the hydrogen generation 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.

本実施形態における金属材料は、水分と接触することによりカプセル20内において水素ガスを発生させる。こうした水分には、水道水、浄水、イオン交換水、精製水、純水、RO水などが含まれるが、これに限るものではない。上述の液体L自体を水分として用いることもできる。また、水分であるから水蒸気などの気体であってもよい。含有成分、硬度、液性の如何にかかわらず、水分を含んでいる液体又は気体であれば本実施形態の水分として用いることができる。   The metal material in the present embodiment generates hydrogen gas in the capsule 20 by coming into contact with moisture. Such water includes, but is not limited to, tap water, purified water, ion exchange water, purified water, pure water, RO water and the like. The liquid L itself can also be used as moisture. Further, since it is moisture, a gas such as water vapor may be used. Any liquid or gas containing water can be used as the water in this embodiment regardless of the content, hardness, and liquidity.

金属材料を含む水素発生剤11と反応させる水分の量の目安としては、後述するように袋体12ごと液体Lに瞬時に浸漬するなど、水素発生体10を収容するカプセル20に水分が残存しない程度の少量であることが望ましい。たとえば、カプセル20内に残存する水分量が10cc以下、好ましくは5cc以下、さらに好ましくは3cc以下、特に好ましくは1cc以下である。こうした余分な水分が袋体12からカプセル20内に流出するのを防止するために、吸水ビーズ、イオン交換樹脂(乾式イオン交換樹脂は吸水性が高くさらに好ましい)、吸水紙、ヒアルロン酸、ポリアクリル酸など吸水性のある物質や材料が、カプセル20内や袋体12などに含まれていることは望ましい。   As a measure of the amount of moisture to be reacted with the hydrogen generator 11 containing a metal material, no moisture remains in the capsule 20 containing the hydrogen generator 10, such as instantly immersing the bag 12 together with the liquid L as described later. A small amount is desirable. For example, the amount of water remaining in the capsule 20 is 10 cc or less, preferably 5 cc or less, more preferably 3 cc or less, and particularly preferably 1 cc or less. In order to prevent such excess water from flowing out from the bag 12 into the capsule 20, water-absorbing beads, ion exchange resins (dry ion exchange resins are more preferred because they have high water absorption), water-absorbing paper, hyaluronic acid, polyacrylic It is desirable that a water-absorbing substance or material such as an acid is contained in the capsule 20 or the bag body 12.

本実施形態のカプセル20は、液体Lと水素発生剤11とを隔離するとともに、水素発生体10で発生した水素ガスを、カプセル20の一方向弁21を介して、液体Lを入れた容器30内に送る。カプセル20を含む本実施形態の生成装置1は、液体Lを入れる容器30とは別個の部材として、又は容器30に事前に組み込まれた構造部として、容器30に収容される。カプセル20を容器30とは別の部材として構成した実施形態を図1に示し、カプセル20を容器30の一部に組み込んだ実施形態を図4に示し、これらの詳細は後述する。   The capsule 20 of the present embodiment isolates the liquid L and the hydrogen generating agent 11, and the container 30 containing the liquid L from the hydrogen gas generated by the hydrogen generator 10 through the one-way valve 21 of the capsule 20. Send in. The generating apparatus 1 according to the present embodiment including the capsule 20 is accommodated in the container 30 as a member separate from the container 30 into which the liquid L is put, or as a structure unit incorporated in the container 30 in advance. An embodiment in which the capsule 20 is configured as a member different from the container 30 is shown in FIG. 1, and an embodiment in which the capsule 20 is incorporated in a part of the container 30 is shown in FIG. 4, and these details will be described later.

本実施形態のカプセル20の第1実施形態を図2A〜図2Dに示す。本実施形態のカプセル20は、カプセル本体22と、バルブキャップ23と、ダックビルバルブ21とを備える。カプセル本体22は、水素発生剤11と水分との反応熱に耐え得る程度の耐熱性を有する樹脂材料から成形された、有底筒状の部材であり、内部に水素発生体10を入れ、上部開口にバルブキャップ23を装着する。カプセル本体22の外表面には、円周方向に沿って所定の間隔をもって設けられた複数の突起片24が一体的に形成されている。この突起片24は、水素発生剤11と水分との反応熱(金属材料の種類にもよるが200℃程度の高温になるものもある)がカプセル本体22から容器30に伝わって、当該容器30を変形させたりすることを防止するための構成である。つまり、突起片24を設け、カプセル20と容器30との接触距離を長くすること及び/又は接触面積を小さくすることで、容器30へ伝わる熱を抑制する。なお、図2A〜図2Dに示す実施形態では、カプセル本体22の外表面に突起片24を設けたが、バルブキャップ23の外表面に突起片を設けてもよい。   A first embodiment of the capsule 20 of the present embodiment is shown in FIGS. 2A to 2D. The capsule 20 of this embodiment includes a capsule body 22, a valve cap 23, and a duckbill valve 21. The capsule body 22 is a bottomed cylindrical member molded from a heat-resistant resin material capable of withstanding the reaction heat between the hydrogen generating agent 11 and moisture, and the hydrogen generator 10 is placed inside the capsule body 22. A valve cap 23 is attached to the opening. On the outer surface of the capsule main body 22, a plurality of protruding pieces 24 provided at predetermined intervals along the circumferential direction are integrally formed. The protrusions 24 are such that reaction heat between the hydrogen generating agent 11 and moisture (some of which may be as high as about 200 ° C. depending on the type of metal material) is transmitted from the capsule body 22 to the container 30, and the container 30. It is the structure for preventing deforming. That is, the protrusion piece 24 is provided, and the heat transmitted to the container 30 is suppressed by increasing the contact distance between the capsule 20 and the container 30 and / or reducing the contact area. In the embodiment shown in FIGS. 2A to 2D, the protruding piece 24 is provided on the outer surface of the capsule body 22, but the protruding piece may be provided on the outer surface of the valve cap 23.

本実施形態のカプセル20のバルブキャップ23は、ダックビルバルブ21を保持するとともに、カプセル本体22の上部開口を閉塞する機能を司る。バルブキャップ23も、カプセル本体22と同様に、水素発生剤11と水分との反応熱に耐え得る程度の耐熱性を有する樹脂材料から成形されている。   The valve cap 23 of the capsule 20 of the present embodiment controls the function of holding the duckbill valve 21 and closing the upper opening of the capsule body 22. Similarly to the capsule body 22, the valve cap 23 is also molded from a heat-resistant resin material that can withstand the heat of reaction between the hydrogen generating agent 11 and moisture.

ダックビルバルブ21は、弾性を有する樹脂材料から成形され、鳥のくちばし状に形成され、先端の稜線部分にスリット25が設けられている。これにより、カプセル20内の内圧が高くなるまでは、ダックビルバルブ21の自己弾性によりスリット25が閉じた状態となり、カプセル20内の内圧が高くなると、自己弾性に抗してダックビルバルブ21のスリットを押し広げて水素ガスが排出される。ダックビルバルブ21が本発明の一方向弁又は逆止弁の一例である。   The duckbill valve 21 is molded from an elastic resin material, is formed in the shape of a bird's beak, and is provided with a slit 25 at the ridge line portion at the tip. Thus, until the internal pressure in the capsule 20 increases, the slit 25 is closed by the self-elasticity of the duckbill valve 21, and when the internal pressure in the capsule 20 increases, the slit of the duckbill valve 21 resists the self-elasticity. Hydrogen gas is discharged by pushing it out. The duckbill valve 21 is an example of a one-way valve or a check valve of the present invention.

なお、一方向弁又は逆止弁の一例であるダックビルバルブ21に代えて、カプセル20の内部で発生した水素ガスはカプセル20の外部へ排出されるが、カプセル20の外部の液体はカプセル20の内部へ導入されない水素ガス透過膜を設けてもよい。また、後述する図4及び図5の他の実施形態にて説明するように、カプセル20を容器30のキャップ32に固定し、図4及び図5の実施形態とは異なるが(同図の実施形態はカプセル20を容器30の外部に設けた)、カプセル20を容器30の内部に入れてもよい。さらに、水素発生剤11が容器30に入れた液体Lに混入しても問題のない場合は、一方向弁、逆止弁、水素ガス透過膜等々に限定されず、カプセル20の内部で発生した水素ガスはカプセル20の外部へ排出され、カプセル20の外部の液体はカプセル20の内部へ導入されるものであってもよい。   Instead of the duckbill valve 21 which is an example of a one-way valve or a check valve, the hydrogen gas generated inside the capsule 20 is discharged to the outside of the capsule 20, but the liquid outside the capsule 20 A hydrogen gas permeable membrane that is not introduced into the interior may be provided. 4 and FIG. 5 to be described later, the capsule 20 is fixed to the cap 32 of the container 30 and is different from the embodiment of FIG. 4 and FIG. The capsule 20 is provided outside the container 30), and the capsule 20 may be placed inside the container 30. Furthermore, when there is no problem even if the hydrogen generating agent 11 is mixed into the liquid L contained in the container 30, it is not limited to a one-way valve, a check valve, a hydrogen gas permeable membrane, etc., and is generated inside the capsule 20. The hydrogen gas may be discharged to the outside of the capsule 20, and the liquid outside the capsule 20 may be introduced into the capsule 20.

本実施形態の容器30は、上述した液体Lを入れる容器であって、その内容物を大気に触れさせないよう工夫が施されている密閉された容器を含む。キャップ付きペットボトルやアルミボトルなど蓋付き容器は密閉された容器に含まれる。密閉された容器30は、人が手に持って振盪しやすいように、ポータブルな形態と容量を備えていることが望ましい。2L以下、好ましくは1L以下、特に好ましくは0.5L以下の容量の密閉された容器30が望ましいが、これに限るものではない。密閉された容器30の材質として好ましいのは、水素透過性が低い容器である。水素透過性が低いほど発生した水素を容器30の外部へ逃すことが少ないからである。   The container 30 according to the present embodiment is a container for containing the liquid L described above, and includes a sealed container in which the contents are not exposed to the atmosphere. Containers with lids such as plastic bottles with caps and aluminum bottles are included in sealed containers. The sealed container 30 preferably has a portable form and capacity so that a person can easily hold it in his hand and shake it. A sealed container 30 having a capacity of 2 L or less, preferably 1 L or less, particularly preferably 0.5 L or less is desirable, but is not limited thereto. A preferable material for the sealed container 30 is a container having low hydrogen permeability. This is because as the hydrogen permeability is lower, the generated hydrogen is less likely to escape to the outside of the container 30.

容器30の水素透過性は次のように測定する。すなわち、特願2009−221567に記載される方法などを参考に、安定的にほぼ飽和濃度(20℃・1気圧で1.6ppm)を保つ水素溶存水を測定対象となる密閉容器内容積の20倍の体積で生成するとともに、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など)を満水充填した該密閉容器を該水素溶存水に5時間浸漬する。その後、該浄水の溶存水素濃度を測定し、溶存水素濃度が1000ppb以下、好ましくは500ppb以下、より好ましくは100ppb以下、特に好ましくは10ppb以下である容器30が、本実施形態の水素透過性が低い容器に含まれる。   The hydrogen permeability of the container 30 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 the container 30 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 has low hydrogen permeability in this embodiment. Contained in a container.

本実施形態の容器30は、密閉性に加えて、水素発生による内圧の上昇に耐えうる耐圧性能を有することが望ましい。絶対圧力で0.11MPa、好ましくは0.4MPa、さらに好ましくは0.5MPa、特に好ましくは0.8MPaの内圧に耐えうる耐圧容器である。炭酸飲料用ペットボトルなどは好適に用いられる。本実施形態の容器30は、安全に開栓できるようキャップを開ける途中で圧力を逃がす機構(ベントスロット)を口部に備えていることが望ましい。   It is desirable that the container 30 of the present embodiment has pressure resistance capable of withstanding an increase in internal pressure due to hydrogen generation in addition to hermeticity. The pressure vessel is 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 container 30 of the present embodiment is provided with a mechanism (vent slot) for releasing pressure while opening the cap so that it can be safely opened.

本実施形態において得られる水素含有液体は、溶存水素濃度が8ppm以上、好ましくは10ppm以上の水素含有液体である。本実施形態において過飽和水素含有液体とは、常温常圧における溶解度(1.6ppm)以上の溶存水素濃度であり、特に8.0ppm以上、9.0ppm以上、10.0ppm以上の高濃度水素含有液体をいう。   The hydrogen-containing liquid obtained in the present embodiment is a hydrogen-containing liquid having a dissolved hydrogen concentration of 8 ppm or more, preferably 10 ppm or more. In the present embodiment, the supersaturated hydrogen-containing liquid is a dissolved hydrogen concentration having a solubility (1.6 ppm) or higher at room temperature and normal pressure, and particularly a high-concentration hydrogen-containing liquid of 8.0 ppm or higher, 9.0 ppm or higher, and 10.0 ppm or higher. Say.

次に、図3A〜図3Hを参照しながら、本実施形態の水素含有液体の生成装置1の使用方法を説明する。
まず、図3Aに示すように、袋体12内にアルミニウムやマグネシウムなどの金属材料及び反応促進剤を含む水素発生剤11を入れた水素発生体10を用意し、図3Bに示すように、たとえば容器30に入れた液体Lに、袋体12が濡れるように5〜6秒程度浸す。次いで、図3Cに示すように、カプセル本体22の中に、先ほど濡らした水素発生体10を入れ、バルブキャップ23で蓋をする。なお、容器30には液体Lを上部開口まで満たしておく。すなわち、容器30のヘッドスペースSにはなるべく空気が入らないように液体Lを満たしておく。
Next, a method of using the hydrogen-containing liquid generating apparatus 1 according to this embodiment will be described with reference to FIGS. 3A to 3H.
First, as shown in FIG. 3A, a hydrogen generator 10 in which a hydrogen generator 11 containing a metal material such as aluminum or magnesium and a reaction accelerator is placed in a bag body 12 is prepared. Immerse in the liquid L in the container 30 for about 5 to 6 seconds so that the bag body 12 gets wet. Next, as shown in FIG. 3C, the hydrogen generator 10 that has already been wetted is placed in the capsule body 22, and the lid is covered with the valve cap 23. The container 30 is filled with the liquid L up to the upper opening. That is, the liquid L is filled in the head space S of the container 30 so that air does not enter as much as possible.

次いで、図3Dに示すように、カプセル20を容器30に入れキャップ32で蓋をする。本実施形態のカプセル20は、液体Lより比重が小さいので容器30の液面に浮くが、液体Lより比重の大きいカプセルを用い、容器30内の液体Lに沈めてもよい。しばらく時間が経つと、水素発生剤11と水分との反応が開始することにより、カプセル20内に水素ガスが発生し、その内圧がある程度上昇してダックビルバルブ21の自己弾性に打ち勝つと、ダックビルバルブ21のスリット25が開き、このスリット25から水素ガスが排出される。ただし、開いたスリット25からカプセル20内に液体Lが入り込むことはない。   Next, as shown in FIG. 3D, the capsule 20 is placed in the container 30 and covered with a cap 32. Since the capsule 20 of this embodiment has a specific gravity smaller than that of the liquid L, it floats on the liquid surface of the container 30. However, a capsule having a specific gravity larger than that of the liquid L may be used and submerged in the liquid L in the container 30. After a while, when the reaction between the hydrogen generating agent 11 and moisture starts, hydrogen gas is generated in the capsule 20, and when the internal pressure rises to some extent to overcome the self-elasticity of the duckbill valve 21, the duckbill valve 21 slit 25 is opened, and hydrogen gas is discharged from the slit 25. However, the liquid L does not enter the capsule 20 from the opened slit 25.

カプセル20の内部からダックビルバルブ21を介して水素ガスが容器30の内部へ排出されると、図3E及び図3Fに示すように、容器30のヘッドスペースS(容器30の上部開口の近傍の空間)に水素ガスが溜まることになる。このとき、カプセル20は、水素発生剤11と水分との反応熱によって比較的高温となっているが、容器30との接触は突起片24にて行われていることから、接触点まで高温の熱が伝わらない。これにより、容器30の変形などを防止することができる。   When hydrogen gas is discharged from the inside of the capsule 20 to the inside of the container 30 through the duckbill valve 21, as shown in FIGS. 3E and 3F, the head space S of the container 30 (the space near the upper opening of the container 30). ) Will accumulate hydrogen gas. At this time, the capsule 20 has a relatively high temperature due to the reaction heat between the hydrogen generating agent 11 and moisture. However, since the contact with the container 30 is performed by the protruding piece 24, the capsule 20 has a high temperature up to the contact point. The heat is not transmitted. Thereby, a deformation | transformation etc. of the container 30 can be prevented.

なおカプセル20内で、水素発生剤11と水分との反応により発生した水素ガスは、ダックビルバルブ21を介して液体Lを入れた容器30内に放出され、ヘッドスペースSに高圧・高濃度の水素ガス相を形成する。なお、本実施形態の生成装置1を液体L中に沈めて設置した場合であっても、発生した水素分子のほとんどは液体Lに溶解することなく、まずは容器30のヘッドスペースの空気相へ移行する。水素発生剤11を袋体12に入れた水素発生体10をカプセル20に入れると、水素ガスは、カプセル20の内部に適量結集した後はじめて、水素ガス気泡としてダックビルバルブ21から排出される。言い換えれば、液体L中に排出されるとき、水素分子は、既にある程度の大きさを有する水素ガス気泡として放出されることから、カプセル20が水素ガスに対する一種のストッパーとして作用するため、液体Lに溶解することなく、まずは容器30のヘッドスペースの空気相へ移行するものと推察される。   The hydrogen gas generated by the reaction between the hydrogen generating agent 11 and moisture in the capsule 20 is released into the container 30 containing the liquid L through the duckbill valve 21 and is supplied to the head space S with high pressure and high concentration hydrogen. A gas phase is formed. Even when the generation device 1 of the present embodiment is placed in the liquid L, most of the generated hydrogen molecules are not dissolved in the liquid L, and first move to the air phase of the head space of the container 30. To do. When the hydrogen generator 10 in which the hydrogen generator 11 is put in the bag body 12 is put in the capsule 20, hydrogen gas is discharged from the duckbill valve 21 as hydrogen gas bubbles only after an appropriate amount is collected inside the capsule 20. In other words, when the hydrogen molecules are discharged into the liquid L, the hydrogen molecules are already released as hydrogen gas bubbles having a certain size, so that the capsule 20 acts as a kind of stopper for the hydrogen gas. It is presumed that the air phase in the head space of the container 30 first shifts without dissolving.

このことは目視でも観察される。たとえば、本実施形態の生成装置1を、液体Lを入れた容器30内に入れ、容器30を横に倒してそのまましばらく放置しておくと、カプセル20内で発生した水素ガスが間歇的にダックビルバルブ21から水素気泡となって放出しながら、水素ガス相の体積を次第に増大させていく。言い換えれば、放出される水素ガスの気泡サイズが大きいものであるため、それは水中を上昇し密閉された容器30のヘッドスペースの気相へと素早く移行する。   This is also observed visually. For example, when the generator 1 of the present embodiment is placed in the container 30 containing the liquid L, the container 30 is laid down and left for a while, the hydrogen gas generated in the capsule 20 is intermittently duck billed. While releasing hydrogen bubbles from the valve 21, the volume of the hydrogen gas phase is gradually increased. In other words, since the bubble size of the released hydrogen gas is large, it rises in water and quickly moves into the gas phase of the head space of the sealed container 30.

従来、水素分子に限らないが、いわゆるバブリングを利用した気体溶解技術においては、ガスの気泡サイズを可能な限り小さくすること、すなわち、気泡が気相へ赴く上昇速度を遅らせることこそが、高濃度のガス溶液を製造するためには重要であると考えられてきた。水素、酸素またはオゾンを含む産業用ガスのマイクロバブル化やナノバブル化は、本願出願時においても、依然として当業界の主要な技術課題の一つとして認識されている。   Conventionally, not only hydrogen molecules, but gas dissolution technology using so-called bubbling is to reduce the bubble size of the gas as much as possible, that is, to slow the rate at which the bubbles go into the gas phase. It has been considered important to produce a gas solution. The formation of microbubbles and nanobubbles of industrial gas containing hydrogen, oxygen or ozone is still recognized as one of the main technical problems in the industry even when the present application is filed.

これに対して、本願発明者等は、家庭、職場、街中、店頭などを含むさまざまな場所で、消費者が使用時に高濃度水素含有液体を生成しようとする機会においては、飲料水、茶、コーヒーなどの飲料を含む液体に水素分子を直接溶解させるよりも、まずは、密閉された容器30内に水素ガス相を形成するとともに容器30の内圧を高め、その後に密閉された容器30を適宜振盪することで気相の水素ガスを回収する方がはるかに望ましいことを知見した。したがって、水素含有液体の溶存水素濃度を高めるためには、図3Gに示すように、本実施形態のカプセル20を密閉された容器30内に入れるとともに、密閉された容器30を適宜振盪することが望ましい。   On the other hand, the inventors of the present application, in various places including homes, workplaces, streets, stores, etc., at the occasion where consumers try to produce high-concentration hydrogen-containing liquids at the time of use, drinking water, tea, Rather than directly dissolving hydrogen molecules in a liquid containing a beverage such as coffee, first, a hydrogen gas phase is formed in the sealed container 30 and the internal pressure of the container 30 is increased, and then the sealed container 30 is shaken appropriately. It was found that it is much more desirable to recover gas phase hydrogen gas. Therefore, in order to increase the dissolved hydrogen concentration of the hydrogen-containing liquid, as shown in FIG. 3G, the capsule 20 of the present embodiment is placed in a sealed container 30 and the sealed container 30 is shaken appropriately. desirable.

本実施形態における振盪は、密閉された容器30に物理的衝撃を与えることにより密閉された容器30内の液体Lと気相にある水素ガスとを接触させつつ、液体L中の溶存酸素など溶存ガスを水素ガスに置換する。本実施形態の振盪は、手を用いた自然的振盪のほか機械を用いた人工的振盪も含まれる。振盪器、攪拌機、超音波発生装置などによる振盪はこうした人工的振盪に含まれる。また、密閉された容器30の気相へ水素ガスが一層蓄積されることを目的に、カプセル20を密閉された容器30内に入れてから、1分経過した後、好ましくは2分経過した後、より好ましくは4分経過した後、さらに好ましくは8分経過した後、特に好ましくは10分経過した後に振盪を開始することが望ましい。また、振盪時間は、高圧・高濃度水素ガスの生体適用液への溶解を促進させるため、自然的振盪で5秒以上、好ましくは10秒以上、より好ましくは15秒以上、さらに好ましくは30秒以上であることが望ましい。また、振盪のし易さを考慮し、生体適用液を充填した後も、密閉容器には容器容量の15%以下、好ましくは10%以下、特に好ましくは5%以下の容量でヘッドスペースが設けられることが望ましい。以上の使用方法により、図3Hに示すように水素含有液体が得られることになる。   In this embodiment, the shaking is performed by dissolving the dissolved oxygen or the like in the liquid L while bringing the liquid L in the sealed container 30 into contact with the hydrogen gas in the gas phase by giving a physical impact to the sealed container 30. The gas is replaced with hydrogen gas. The shaking in the present embodiment includes not only natural shaking using a hand but also artificial shaking using a machine. Shaking with a shaker, stirrer, ultrasonic generator, etc. is included in such artificial shaking. In addition, for the purpose of further accumulating hydrogen gas in the gas phase of the sealed container 30, 1 minute has passed since the capsule 20 was put in the sealed container 30, preferably 2 minutes later. More preferably, after 4 minutes have passed, more preferably after 8 minutes, and particularly preferably after 10 minutes, it is desirable to start shaking. Further, the shaking time is 5 seconds or more, preferably 10 seconds or more, more preferably 15 seconds or more, more preferably 30 seconds by natural shaking in order to promote the dissolution of high-pressure and high-concentration hydrogen gas in the biological application liquid. The above is desirable. In consideration of ease of shaking, the sealed container is 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 even after filling with the biological application liquid. It is desirable that By the above usage method, a hydrogen-containing liquid is obtained as shown in FIG. 3H.

図4は、本発明に係る水素含有液体の生成装置1の他の実施の形態を示す構成部品図、図5は、図4に示す水素含有液体の生成装置1の使用方法を示す図(図3D,図3Eに相当する)である。同図に示す生成装置1は、カプセル20を容器30の一部に組み込んだ実施形態であり、具体的には図4に示すように、容器30のキャップ32にカプセル20が設けられ、図5に示すように容器30にキャップ32を装着すると、容器30の外部から容器30の内部へ水素ガスを放出することになる。すなわち、図3D及び図3Eに示すように、カプセル20を容器30内に入れなくても、容器30の内部へ水素ガスを供給する。   FIG. 4 is a component diagram showing another embodiment of the hydrogen-containing liquid generating apparatus 1 according to the present invention, and FIG. 5 is a diagram showing a method of using the hydrogen-containing liquid generating apparatus 1 shown in FIG. 3D, corresponding to FIG. 3E). The generating apparatus 1 shown in the figure is an embodiment in which the capsule 20 is incorporated in a part of the container 30. Specifically, as shown in FIG. 4, the capsule 20 is provided in a cap 32 of the container 30, and FIG. When the cap 32 is attached to the container 30 as shown in FIG. 3, hydrogen gas is released from the outside of the container 30 to the inside of the container 30. That is, as shown in FIGS. 3D and 3E, hydrogen gas is supplied into the container 30 without the capsule 20 being placed in the container 30.

さて、以上のような構成及び使用方法の生成装置1において、本願発明者らは、溶存水素濃度が7ppmの水素含有液体を生成することに成功した。ただし、同様の条件で水素濃度が8ppm、特に10ppmを超える水素含有液体を生成するには至らなかった。尤も、水素発生剤11の重量を増加させれば水素ガスの発生量も増加するので溶存水素濃度を高くすることは可能であるが、上述した使用方法から理解できるとおり、水素ガスの発生量が多くなると容器30内の内圧も高くなる。そのため、高耐圧の容器30が必要となる。また、水素発生剤11の重量を増加させるにしても、未反応の金属材料が残り無駄が生じてはならない。そこで、本発明者らは鋭意検討及び試行錯誤を繰り返した結果、水素発生剤11の重量W(モル数でも等価)と、カプセル20の容積V(カプセル本体22、バルブキャップ23及びダックビルバルブ21を含む内部の容積)との関係を所定値にすると、適度な水素発生剤11の重量で、溶存水素濃度が8ppmを超える水素含有液体を得ることに成功した。以下、本発明の実施例及び比較例を説明する。   The inventors of the present invention have succeeded in generating a hydrogen-containing liquid having a dissolved hydrogen concentration of 7 ppm in the generation apparatus 1 having the above-described configuration and usage method. However, no hydrogen-containing liquid having a hydrogen concentration exceeding 8 ppm, particularly 10 ppm, was produced under the same conditions. However, if the weight of the hydrogen generating agent 11 is increased, the amount of hydrogen gas generated also increases, so it is possible to increase the dissolved hydrogen concentration. However, as can be understood from the method of use described above, the amount of hydrogen gas generated is low. As the number increases, the internal pressure in the container 30 also increases. Therefore, a high pressure resistant container 30 is required. Moreover, even if the weight of the hydrogen generating agent 11 is increased, unreacted metal material remains and should not be wasted. Accordingly, as a result of repeated intensive studies and trial and error, the present inventors have determined that the weight W of the hydrogen generating agent 11 (equivalent to the number of moles) and the volume V of the capsule 20 (the capsule body 22, the valve cap 23, and the duckbill valve 21). When the relationship with the internal volume) is set to a predetermined value, a hydrogen-containing liquid having a dissolved hydrogen concentration exceeding 8 ppm was successfully obtained with an appropriate weight of the hydrogen generating agent 11. Examples of the present invention and comparative examples will be described below.

《実施例1》
金属材料としての、金属アルミニウム末(和光純薬工業株式会社製、粒径は53〜150μm、80%up)と水酸化カルシウム(和光純薬工業株式会社製)とを、金属アルミニウム末が75重量%、水酸化カルシウムが25重量%の割合で混合し、0.66gの水素発生剤11を得た。この水素発生剤0.66gを不織布(旭化成株式会社製プレシゼRegular C5160)に包み込み、ヒートシールすることで水素発生体10を得た。また、口部までの満水充填容量が約530ccの炭酸飲料用ペットボトル30を用意し、これに藤沢市水道水(水温が14.6℃)を満タンに充填した。
内部の容積が5.4mlのカプセル20を用意し、図3Bに示すように上記水素発生体10を、ペットボトル30に入れた水道水に5〜6秒浸漬して湿らせたのち、この水素発生体10をカプセル本体22に入れ、バルブキャップ23で蓋をした。そして、図3Dに示すように、カプセル20をペットボトル30に入れ、キャップ32で蓋をした。同じものを6セット用意した。
10分放置後及び24時間放置後のそれぞれにつき、発明者の一人(平均的体格を有する日本人30代男性)がペットボトル中腹部を利手に保持し、手首のみを左右に動かすことでキャップが手首上空に半円の弧を描くように、2往復/秒のペースで120往復し、振盪した(合計60秒)。その後、それぞれの内容液体Lの溶存水素濃度を測定した。この結果を表1及び図6に示す。なお、溶存水素濃度判定試薬は、MiZ株式会社製の溶存水素判定試薬(エタノール、メチレンブルー及び白金コロイドを含むアルコール類9.88ml)を使用して溶存水素濃度を滴定した。
Example 1
Metallic aluminum powder (manufactured by Wako Pure Chemical Industries, Ltd., particle size is 53 to 150 μm, 80% up) and calcium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) as metal materials, and metal aluminum powder of 75 wt. % And calcium hydroxide were mixed at a ratio of 25% by weight to obtain 0.66 g of the hydrogen generator 11. The hydrogen generator 10 was obtained by wrapping 0.66 g of this hydrogen generator in a non-woven fabric (Precise Regular C5160 manufactured by Asahi Kasei Corporation) and heat-sealing. In addition, a PET bottle 30 for carbonated drink having a full water filling capacity up to the mouth was prepared, and this was filled with Fujisawa city tap water (water temperature 14.6 ° C.) in a full tank.
A capsule 20 having an internal volume of 5.4 ml is prepared. As shown in FIG. 3B, the hydrogen generator 10 is dipped in tap water placed in a PET bottle 30 for 5 to 6 seconds and moistened. The generator 10 was placed in the capsule body 22 and covered with a valve cap 23. And as shown to FIG. 3D, the capsule 20 was put into the PET bottle 30, and the cap 32 was covered. Six sets of the same were prepared.
After leaving for 10 minutes and 24 hours, one of the inventors (a male in his 30s with an average physique) holds the middle of a plastic bottle in his hand and moves the wrist only to the left and right. Shook and swung (total 60 seconds) at a rate of 2 reciprocations / second so that a semicircular arc was drawn over the wrist. Then, the dissolved hydrogen concentration of each content liquid L was measured. The results are shown in Table 1 and FIG. In addition, the dissolved hydrogen concentration determination reagent titrated the dissolved hydrogen concentration using the dissolved hydrogen determination reagent (ethanol, methylene blue, and alcohol containing platinum colloid 9.88ml) by MiZ Corporation.

《実施例2》
水素発生体10及びペットボトル30は同じ条件とし、カプセル20の内部の容積を、7.5mlとしたものを用意し、上記実施例1と同じ条件で得られた内容液体Lの溶存水素濃度を測定した。この結果を表1及び図6に示す。
Example 2
The hydrogen generator 10 and the PET bottle 30 have the same conditions, and the capsule 20 has an internal volume of 7.5 ml, and the dissolved hydrogen concentration of the content liquid L obtained under the same conditions as in Example 1 is set. It was measured. The results are shown in Table 1 and FIG.

《比較例1》
水素発生剤11及びペットボトル30は同じ条件とし、カプセル20の内部の容積を、11.0mlとしたものを用意し、上記実施例1と同じ条件で得られた内容液体Lの溶存水素濃度を測定した。この結果を表1及び図6に示す。
<< Comparative Example 1 >>
The hydrogen generating agent 11 and the PET bottle 30 have the same conditions, and the capsule 20 has an internal volume of 11.0 ml. The dissolved hydrogen concentration of the content liquid L obtained under the same conditions as in Example 1 is set. It was measured. The results are shown in Table 1 and FIG.

《比較例2》
水素発生剤11及びペットボトル30は同じ条件とし、カプセル20の内部の容積を、13.5mlとしたものを用意し、上記実施例1と同じ条件で得られた内容液体Lの溶存水素濃度を測定した。この結果を表1及び図6に示す。
<< Comparative Example 2 >>
The hydrogen generating agent 11 and the PET bottle 30 have the same conditions, and the capsule 20 has an internal volume of 13.5 ml, and the dissolved hydrogen concentration of the content liquid L obtained under the same conditions as in Example 1 is set. It was measured. The results are shown in Table 1 and FIG.

Figure 2017104842
Figure 2017104842

《考 察》
上記実施例1,2及び比較例1,2の溶存水素濃度の変化率(1階微分値)を取ると、10分後の溶存水素濃度において、実施例2と比較例1との間に有意差がみられ、24時間後の溶存水素濃度において、実施例1と実施例2との間に有意差がみられた。よって、10分後の溶存水素濃度を6ppm以上にするには水素発生剤11の重量(Wg)に対するカプセル20の容積(Vml)の比率(V/W)を、11.4以下にすることが好ましい。この場合に、24時間後の溶存水素濃度が8ppmを超えることになる。また、24分後の溶存水素濃度を10ppm以上にするには水素発生剤11の重量(Wg)に対するカプセル20の容積(Vml)の比率(V/W)を、8.2以下にすることが好ましい。
《Discussion》
Taking the rate of change of the dissolved hydrogen concentration in Examples 1 and 2 and Comparative Examples 1 and 2 (first-order differential value), it was significant between Example 2 and Comparative Example 1 in the dissolved hydrogen concentration after 10 minutes. A difference was observed, and a significant difference was observed between Example 1 and Example 2 in the dissolved hydrogen concentration after 24 hours. Therefore, in order to increase the dissolved hydrogen concentration after 10 minutes to 6 ppm or more, the ratio (V / W) of the volume (Vml) of the capsule 20 to the weight (Wg) of the hydrogen generating agent 11 should be 11.4 or less. preferable. In this case, the dissolved hydrogen concentration after 24 hours exceeds 8 ppm. In order to make the dissolved hydrogen concentration after 24 minutes 10 ppm or more, the ratio (V / W) of the volume (Vml) of the capsule 20 to the weight (Wg) of the hydrogen generator 11 should be 8.2 or less. preferable.

《実施例3》
実施例1における水素発生体10の水素発生剤11を0.65g、炭酸飲料用ペットボトル30の口部までの満水充填容量を300ml、カプセル20の内部の容積を5.3mlとしたこと以外は実施例1と同じ条件で水素含有液体を生成し、得られた内容液体Lの溶存水素濃度を測定した。この結果を表2及び図7に示す。
Example 3
Except that the hydrogen generating agent 11 of the hydrogen generator 10 in Example 1 was 0.65 g, the full water filling capacity up to the mouth of the carbonated beverage PET bottle 30 was 300 ml, and the internal volume of the capsule 20 was 5.3 ml. A hydrogen-containing liquid was produced under the same conditions as in Example 1, and the dissolved hydrogen concentration of the obtained content liquid L was measured. The results are shown in Table 2 and FIG.

《実施例4》
水素発生体10及びペットボトル30は実施例3と同じ条件とし、カプセル20の内部の容積を、7.4mlとしたものを用意し、上記実施例3と同じ条件で得られた内容液体Lの溶存水素濃度を測定した。この結果を表2及び図7に示す。
Example 4
The hydrogen generator 10 and the PET bottle 30 were prepared under the same conditions as in Example 3, and the capsule 20 was prepared with an internal volume of 7.4 ml. The content liquid L obtained under the same conditions as in Example 3 was prepared. The dissolved hydrogen concentration was measured. The results are shown in Table 2 and FIG.

《比較例3》
水素発生体10及びペットボトル30は実施例3と同じ条件とし、カプセル20の内部の容積を、10.9mlとしたものを用意し、上記実施例3と同じ条件で得られた内容液体Lの溶存水素濃度を測定した。この結果を表2及び図7に示す。
<< Comparative Example 3 >>
The hydrogen generator 10 and the plastic bottle 30 were prepared under the same conditions as in Example 3, and the capsule 20 was prepared with a volume of 10.9 ml. The content liquid L obtained under the same conditions as in Example 3 was prepared. The dissolved hydrogen concentration was measured. The results are shown in Table 2 and FIG.

《比較例4》
水素発生体10及びペットボトル30は実施例3と同じ条件とし、カプセル20の内部の容積を、13.3mlとしたものを用意し、上記実施例3と同じ条件で得られた内容液体Lの溶存水素濃度を測定した。この結果を表2及び図7に示す。
<< Comparative Example 4 >>
The hydrogen generator 10 and the PET bottle 30 were prepared under the same conditions as in Example 3, and the capsule 20 was prepared with a volume of 13.3 ml. The content of liquid L obtained under the same conditions as in Example 3 was prepared. The dissolved hydrogen concentration was measured. The results are shown in Table 2 and FIG.

Figure 2017104842
Figure 2017104842

《考 察》
上記実施例3,4及び比較例3,4の溶存水素濃度の変化率(1階微分値)を取ると、10分後の溶存水素濃度において、実施例4と比較例3との間に有意差がみられ、24時間後の溶存水素濃度において、実施例4と比較例3との間に有意差がみられた。よって、10分後の溶存水素濃度を6ppm以上にするには水素発生剤11の重量(Wg)に対するカプセル20の容積(Vml)の比率(V/W)を、少なくとも11.4以下にすることが好ましい。この場合に、24時間後の溶存水素濃度が8ppmを超えることになる。また、24分後の溶存水素濃度を10ppm以上にするには水素発生剤11の重量(Wg)に対するカプセル20の容積(Vml)の比率(V/W)を、8.2以下にすることが好ましい。
《Discussion》
Taking the rate of change of the dissolved hydrogen concentration (first-order differential value) in Examples 3 and 4 and Comparative Examples 3 and 4, there was a significant difference between Example 4 and Comparative Example 3 in the dissolved hydrogen concentration after 10 minutes. A difference was observed, and a significant difference was observed between Example 4 and Comparative Example 3 in the dissolved hydrogen concentration after 24 hours. Therefore, to increase the dissolved hydrogen concentration after 10 minutes to 6 ppm or more, the ratio (V / W) of the volume (Vml) of the capsule 20 to the weight (Wg) of the hydrogen generating agent 11 should be at least 11.4 or less. Is preferred. In this case, the dissolved hydrogen concentration after 24 hours exceeds 8 ppm. In order to make the dissolved hydrogen concentration after 24 minutes 10 ppm or more, the ratio (V / W) of the volume (Vml) of the capsule 20 to the weight (Wg) of the hydrogen generator 11 should be 8.2 or less. preferable.

1…水素含有液体の生成装置
10…水素発生体
11…水素発生剤
12…袋体
20…カプセル
21…ダックビルバルブ(一方向弁、逆止弁又はガス透過膜)
22…カプセル本体
23…バルブキャップ
24…突起片
25…スリット
30…容器
31…容器本体
32…キャップ
L…水素ガスを含有させる液体
DESCRIPTION OF SYMBOLS 1 ... Production apparatus of hydrogen containing liquid 10 ... Hydrogen generator 11 ... Hydrogen generator 12 ... Bag body 20 ... Capsule 21 ... Duck bill valve (one-way valve, check valve or gas permeable membrane)
22 ... Capsule body 23 ... Valve cap 24 ... Projection piece 25 ... Slit 30 ... Container 31 ... Container body 32 ... Cap L ... Liquid containing hydrogen gas

本発明は、水分と反応して水素ガスを発生する水素発生剤と、前記水素発生剤が収納され、内部で発生した水素ガスを外部へ排出されるカプセルと、前記カプセルの内部で発生した水素ガスの添加対象たる液体を収納する容器と、を備える水素含有液体の生成装置において、530ml以下の液体に対し、前記水素発生剤の重量(Wg)に対する前記カプセルの容積(Vml)の比率(V/W)を、8.2以下に設定することにより、上記課題を解決する。 The present invention relates to a hydrogen generating agent that reacts with moisture to generate hydrogen gas, a capsule that contains the hydrogen generating agent and discharges the hydrogen gas generated inside, and hydrogen generated inside the capsule. In a hydrogen-containing liquid production apparatus comprising a container for containing a liquid to which gas is to be added, a ratio (Vml) of the capsule volume (Vml) to the weight (Wg) of the hydrogen generating agent with respect to 530 ml or less of liquid (V / W) , 8 . By setting the number to 2 or less, the above problem is solved.

Claims (8)

水分と反応して水素ガスを発生する水素発生剤と、
前記水素発生剤を入れ、内部で発生した水素ガスを外部へ排出されるカプセルと、
前記カプセルの内部で発生した水素ガスの添加対象たる液体を入れる容器と、を備え、
前記水素発生剤の重量(Wg)に対する前記カプセルの容積(Vml)の比率(V/W)を、11.4以下とした水素含有液体の生成装置。
A hydrogen generating agent that reacts with moisture to generate hydrogen gas;
Capsules that contain the hydrogen generating agent and discharge the hydrogen gas generated inside to the outside,
A container for storing a liquid to which hydrogen gas generated in the capsule is added, and
An apparatus for producing a hydrogen-containing liquid, wherein a ratio (V / W) of a volume (Vml) of the capsule to a weight (Wg) of the hydrogen generating agent is 11.4 or less.
請求項1に記載の水素含有液体の生成装置において、
前記比率を8.2以下とした水素含有液体の生成装置。
The apparatus for producing a hydrogen-containing liquid according to claim 1,
An apparatus for producing a hydrogen-containing liquid, wherein the ratio is 8.2 or less.
請求項1又は2に記載の水素含有液体の生成装置において、
前記水素発生剤は、水素よりイオン化傾向が大きい金属材料又は水素化化合物と反応促進剤とを含み、
前記水素発生剤を水が透過する袋体に入れた状態で前記カプセルに入れる水素含有液体の生成装置。
The hydrogen-containing liquid producing apparatus according to claim 1 or 2,
The hydrogen generator includes a metal material or hydrogenated compound having a higher ionization tendency than hydrogen and a reaction accelerator,
An apparatus for producing a hydrogen-containing liquid, wherein the hydrogen generating agent is placed in the capsule in a state where the hydrogen generating agent is placed in a bag body through which water passes.
請求項1〜3のいずれか一項に記載の水素含有液体の生成装置において、
前記カプセルは、前記水素発生剤を入れる有底筒状のカプセル本体と、前記カプセル本体の開口を閉塞するバルブキャップとを有し、
前記カプセル本体又は前記バルブキャップの外表面に、当該外表面から外方へ突出する突起片が設けられている水素含有液体の生成装置。
In the hydrogen-containing liquid generator according to any one of claims 1 to 3,
The capsule has a bottomed cylindrical capsule body into which the hydrogen generating agent is placed, and a valve cap that closes the opening of the capsule body.
An apparatus for producing a hydrogen-containing liquid, wherein a projection piece projecting outward from the outer surface is provided on an outer surface of the capsule body or the valve cap.
前記容器の容量が、300ml〜530mlである請求項1〜4のいずれか一項に記載の水素含有液体の生成装置。   The capacity | capacitance of the said container is 300 ml-530 ml, The production | generation apparatus of the hydrogen containing liquid as described in any one of Claims 1-4. 請求項1〜5のいずれか一項に記載の生成装置を用いて水素を含有する液体を生成する方法であって、
前記容器に、水素を含有させるべき液体を入れ、
前記水素発生剤に水分を含ませ、
前記水素発生剤を前記カプセルの内部に入れ、
前記容器に前記カプセルを入れて前記容器を密閉し、
所定時間放置する水素含有液体の生成方法。
A method for producing a liquid containing hydrogen using the production apparatus according to any one of claims 1 to 5,
In the container, put a liquid to contain hydrogen,
Moisture is contained in the hydrogen generator,
Putting the hydrogen generating agent inside the capsule;
Put the capsule in the container and seal the container,
A method for producing a hydrogen-containing liquid that is allowed to stand for a predetermined time.
請求項6に記載の水素含有液体の生成方法において、
前記容器を密閉した状態で所定時間放置したのち、前記容器を振盪する水素含有液体の生成方法。
The method for producing a hydrogen-containing liquid according to claim 6,
A method for producing a hydrogen-containing liquid in which the container is left standing for a predetermined time in a sealed state and then the container is shaken.
水分と反応して水素ガスを発生する水素発生剤と、
前記水素発生剤を入れ、内部で発生した水素ガスを外部へ排出されるカプセルと、を備え、
前記カプセルの内部で発生した水素ガスの添加対象たる液体を容器に入れて水素含有液体を生成する水素含有液体の生成キットであって、
前記水素発生剤の重量(Wg)に対する前記カプセルの容積(Vml)の比率(V/W)を、11.4以下とした水素含有液体の生成キット。
A hydrogen generating agent that reacts with moisture to generate hydrogen gas;
A capsule that contains the hydrogen generating agent and discharges hydrogen gas generated inside to the outside;
A hydrogen-containing liquid production kit for producing a hydrogen-containing liquid by adding a liquid to which hydrogen gas generated inside the capsule is added into a container,
A kit for producing a hydrogen-containing liquid, wherein a ratio (V / W) of a volume (Vml) of the capsule to a weight (Wg) of the hydrogen generating agent is 11.4 or less.
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