WO2016104007A1 - Hydrogen production device and hydrogen generation vessel - Google Patents

Hydrogen production device and hydrogen generation vessel Download PDF

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Publication number
WO2016104007A1
WO2016104007A1 PCT/JP2015/082740 JP2015082740W WO2016104007A1 WO 2016104007 A1 WO2016104007 A1 WO 2016104007A1 JP 2015082740 W JP2015082740 W JP 2015082740W WO 2016104007 A1 WO2016104007 A1 WO 2016104007A1
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Prior art keywords
hydrogen
wall portion
peripheral wall
water
aluminum
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PCT/JP2015/082740
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French (fr)
Japanese (ja)
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平尾　一之
浩二 永嶋
瞭介 珍坂
石坂　整
阪井　敦
崇 佐伯
高村　誠
貞雅 藤井
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国立大学法人京都大学
ローム株式会社
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Publication of WO2016104007A1 publication Critical patent/WO2016104007A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/08—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents with metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a hydrogen production apparatus used as fuel for fuel cells and the like, and a hydrogen generation container used in the production apparatus, and more particularly to a hydrogen production apparatus and a hydrogen generation container using a reaction between aluminum and water.
  • a fuel cell is one of the power generation devices that extract electric power through a chemical reaction between hydrogen and oxygen. Compared with existing power generation devices, the power generation efficiency is very high, and noise and vibration are low. In addition, since it emits almost no environmental pollutants, it is expected to be used in various fields such as portable devices such as notebook computers and mobile phones, home appliances, and automobiles. In such a fuel cell, the reduction of the manufacturing cost of hydrogen gas used as a fuel and the improvement of production efficiency are problems.
  • Patent Document 1 discloses a method for producing hydrogen gas by bringing a hydrogen generator containing particulate aluminum and calcium hydroxide into contact with water.
  • a hydrogen generator containing particulate aluminum and calcium hydroxide since relatively inexpensive metal aluminum is used as the hydrogen generating agent, the manufacturing cost can be reduced.
  • an insoluble layer (aluminum oxide or a passive layer of aluminum hydroxide) formed on the particle surface by the reaction of aluminum and water is solubilized with calcium hydroxide to form an unreacted aluminum metal surface. , Increase the efficiency of hydrogen generation.
  • An object of the present invention is to provide a hydrogen production apparatus and a hydrogen generation vessel in which handling of materials for generating hydrogen is easy.
  • the present inventor has used a sheet-like aluminum not designated as a hazardous material in the Japanese Fire Service Act as a hydrogen generating material, thereby allowing a long period of hydrogen generation reaction. It has been found that it is important to improve the hydrogen generation efficiency that it can be sustained, and how efficiently the sheet-like aluminum is brought into contact with water and calcium hydroxide.
  • the present invention has been made based on such new findings.
  • the hydrogen production apparatus which has been made to solve the above problems,
  • An apparatus for producing hydrogen gas using a reaction between water and metal aluminum a) a hydrogen generation container including a cylindrical outer peripheral wall portion and a cylindrical inner peripheral wall portion that is disposed inside the outer peripheral wall portion and forms an annular space between the outer peripheral wall portion; b) one or more sheet-like aluminum accommodated in the annular space in a vertically placed state; c) granular calcium hydroxide contained in the hydrogen generation vessel; d) a water supply port for supplying water into the hydrogen generation container provided in the hydrogen generation container; e) a hydrogen outlet provided in the hydrogen generation container so as to be positioned above the annular space.
  • the hydrogen production apparatus of the present invention when water and calcium hydroxide are accommodated in a hydrogen generation container in which sheet-like aluminum is placed in a vertical state in an annular space, a part of calcium hydroxide is dissolved in water. At this time, hydrogen (gas) is generated by the following reaction (1) between water and aluminum. 2Al + 6H 2 O ⁇ 2Al (OH) 3 + 3H 2 (1)
  • the “longitudinal state” refers to a state in which the sheet-like aluminum is substantially perpendicular to the horizontal plane. Since hydrogen is hardly dissolved in water and lighter than air, hydrogen generated by the reaction between water and sheet-like aluminum rises in the water in the hydrogen generation container and is taken out from the hydrogen outlet to the outside of the hydrogen generation container.
  • the space where the sheet-like aluminum and water react is an annular space
  • the reaction heat can be released from both the outer peripheral wall portion and the inner peripheral wall portion of the annular space, and the heat dissipation effect is improved. For this reason, it is possible to prevent the temperature of the reaction space from rising excessively, and to suppress a decrease in the reaction rate.
  • the hydrogen production apparatus it is preferable to include a pressure maintaining means for maintaining the pressure in the hydrogen generation container below 1 MPa. According to such a configuration, it is not necessary to be regulated by laws and regulations such as the Japanese High Pressure Gas Safety Act when installing the hydrogen production apparatus or operating the hydrogen production apparatus, so that handling becomes easy. .
  • roll-shaped aluminum obtained by winding a single sheet-shaped aluminum a plurality of times so as to surround the inner peripheral wall portion may be accommodated in the annular space.
  • sheet-like aluminum (roll-like aluminum) can be hold
  • a spacer may be interposed between the layers of the rolled aluminum. According to such a configuration, a gap can be surely formed between each layer of rolled aluminum, so that the reaction efficiency between aluminum and water can be further improved. In addition, there is an effect that hydrogen passages generated by the reaction between aluminum and water can be secured between the layers of roll aluminum.
  • the spacer is made of a water-absorbing material and the granular calcium hydroxide is held in the spacer, water containing calcium hydroxide can be present between the respective layers of the rolled aluminum. For this reason, it can further prevent that the passive layer of aluminum oxide or aluminum hydroxide is formed on the surface of aluminum.
  • the configuration in which a spacer is interposed between each layer of roll-shaped aluminum can be realized, for example, by preparing sheet-shaped aluminum and a sheet-shaped spacer of approximately the same size, and superimposing both and winding them a plurality of times.
  • sheet-like spacer paper, cloth, nonwoven fabric or the like excellent in water absorption can be used. Cotton, sponge, or the like may be used as the spacer.
  • the hydrogen generation container includes a bottomed cylindrical container body having an upper opening, and a lid that closes the upper opening of the container body, and enters the container body. It is good to comprise from the cover part which has a bottom cylindrical recessed part.
  • the side wall part of the said container main body comprises the said outer peripheral wall part
  • the side wall part of the recessed part of the said cover part comprises the said inner peripheral wall part.
  • the cooling device includes a first water-cooled pipe wound along the outer surface of the outer peripheral wall portion and circulating the cooling water, and a first water-cooled pipe wound along the outer surface of the inner peripheral wall portion. It can be composed of two water-cooled tubes.
  • a hydrogen generation container which has been made to solve the above problems, has an annular space between a cylindrical outer peripheral wall portion and the outer peripheral wall portion arranged inside the outer peripheral wall portion.
  • a cylindrical inner peripheral wall part forming Water and a hydrogen generating agent are accommodated in the annular space, and hydrogen is generated by a reaction between the water and the hydrogen generating agent.
  • hydrogen gas can be generated continuously for a long time by using sheet-like aluminum in place of granular aluminum conventionally used in a hydrogen production apparatus utilizing the reaction between aluminum and water.
  • a hydrogen generation container having a shape suitable for accommodating sheet-like aluminum that is, an annular space is formed between the cylindrical outer peripheral wall portion and the outer peripheral wall portion disposed inside the outer peripheral wall portion. Since a hydrogen generation container having a cylindrical inner peripheral wall portion is used and one or a plurality of sheet-like aluminum is accommodated vertically in the annular space, the reaction efficiency of water and aluminum, that is, the hydrogen generation efficiency Can be improved.
  • FIG. 1 is a schematic diagram showing the overall configuration of the hydrogen production apparatus of this example.
  • the hydrogen production apparatus 1 connects the hydrogen generator 10, the hydrogen purifier 20 for removing impurities from the hydrogen generated in the hydrogen generator 10, and the hydrogen reservoir 30 for storing the purified hydrogen. It consists of piping.
  • the hydrogen generator 10 includes a hydrogen generation container 11 and a cooler 12 for cooling the hydrogen generation container 11.
  • a gas outlet 13, a safety valve port 14 (manual type), a safety valve port (pressure sensing type) 15, and a water injection port 16 are respectively provided on the upper part of the hydrogen generation container 11, and a probe for the temperature detector 40 is attached.
  • One mounting port 17 is provided.
  • a hydrogen purifier 20 is connected to the gas outlet 13, which is a hydrogen outlet, via pipes 41 and 45.
  • a drain port 18 is provided at the lower part of the hydrogen generation container 11.
  • the pressure in the hydrogen generation container 11 is monitored from the gas outlet 13 via the pressure gauge 42. When the internal pressure of the hydrogen generating container 11 exceeds 1 MPa, a signal from the pressure gauge 42 is received and the valve 42a is opened and exhausted.
  • the configuration of the hydrogen generation container 11 and the cooler 12 will be described later.
  • the hydrogen purifier 20 is filled with a desiccant (not shown) such as zeolite (trade name: molecular sieve) or silica gel in a cylindrical container 23 having an inlet 21 at the lower end and an outlet 22 at the upper end. Configured.
  • the pipe 45 is connected to the inlet 21 of the hydrogen purifier 20, and the hydrogen reservoir 30 is connected to the outlet 22 via a pipe 46.
  • a gas control valve 47 is attached to the pipe 45, and the flow rate of hydrogen gas from the hydrogen generator 10 toward the hydrogen purifier 20 is adjusted so that the internal pressure of the hydrogen generation vessel 11 does not exceed 1 MPa.
  • the internal pressure of the hydrogen generating container 11 is maintained at less than 1 MPa by the pressure gauge 42, the valve 42a, and the gas regulating valve 47, so that the hydrogen producing apparatus 1 or the hydrogen producing apparatus 1 is installed. It is not necessary to be regulated by the High Pressure Gas Safety Law when operating For this reason, handling of the hydrogen production apparatus 1 becomes easy.
  • a drain pipe 24 for discharging water accumulated in the cylindrical container 23 is connected to the lower end surface of the cylindrical container 23.
  • the hydrogen reservoir 30 includes a cartridge-type hydrogen storage container 32 having a hydrogen inlet 31, a pipe 33 that is detachably connected to the hydrogen inlet 31, and a mass flow meter that monitors the hydrogen flow rate provided in the pipe 33. 34.
  • a hydrogen storage alloy (not shown) is accommodated in the hydrogen storage container 32.
  • the pipe 33 is connected to the pipe 46.
  • the pipe 33 When storing hydrogen in the hydrogen storage container 32, the pipe 33 is connected to the hydrogen inlet 31. Thereby, the hydrogen gas from which moisture has been removed by the hydrogen purifier 20 is introduced into the hydrogen storage container 32 through the pipe 46 and the pipe 33 and is absorbed by the hydrogen storage alloy.
  • the hydrogen storage container 32 that has completed the absorption of hydrogen is stored as a hydrogen source by removing the pipe 33 from the hydrogen inlet 31 and sealing the inlet 31. Further, by connecting the hydrogen inlet 31 of another new hydrogen storage container 32 to the pipe 33, the hydrogen generated in the hydrogen generator 10 can be stored again in the hydrogen storage container 32.
  • the hydrogen storage container 32 in which hydrogen is stored can supply hydrogen absorbed in the hydrogen storage alloy as fuel for the fuel cell, for example, by connecting to the fuel cell unit.
  • a hydrogen storage alloy capable of absorbing and releasing hydrogen without cooling or heating the hydrogen storage container 32. Also, using a hydrogen storage alloy that can release hydrogen at the same pressure as during hydrogen storage under the same temperature conditions as during storage of hydrogen, it is not necessary to consume power when releasing hydrogen, which is easy to use.
  • Examples of such a hydrogen storage container 32 include “hydrogen storage alloy canister” manufactured by YMC Co., Ltd.
  • a plug valve, a pressure regulating valve, a flow regulating valve, a safety valve, etc. are attached to appropriate portions of the pipes 41, 43 to 46 and the drain pipe 24 in addition to the above. .
  • the hydrogen generation container 11 includes a cylindrical container body 111 and a lid portion 112 that closes an upper opening of the container body 111.
  • An annular flange 113 is attached to the upper outer periphery of the container main body 111, and the drain port 18 is provided at the lower part of the container main body 111.
  • the lid portion 112 has a cylindrical concave portion 114 having a hemispherical bottom surface and an annular flange 115 provided on the upper outer periphery of the concave portion 114.
  • the outer diameter of the flange 115 is designed to be almost the same as the outer diameter of the flange 113 of the container body 111, and the inner diameter of the flange 115 (that is, the diameter of the recess 114) is slightly smaller than the inner diameter of the flange 113 (that is, the diameter of the container body 111). Designed.
  • the recess 114 enters the inside of the container body 111, and the recess 114 and the side wall of the container body 111
  • the size of the concave portion 114 is set so that an annular space is formed between the concave portions 114 and the concave space is formed between the concave portion 114 and the bottom surface of the container body 111.
  • the space between the concave portion 114 and the side wall portion of the container main body 111 is referred to as an annular space 116.
  • the gas inlet 13, gas outlet 14, safety valve port 15, water injection port 16, and mounting port described above are located in the upper portion of the annular space 116 in the flange 115. 17 is provided.
  • the lower surface of the recess 114 has a hemispherical shape, but may be a flat surface similar to the bottom surface of the container body 111.
  • the coiled first cooling pipe 121 and the coiled second cooling pipe 122 are respectively wound around the outer peripheral surface of the side wall portion of the container body 111 and the inner peripheral surface of the side wall portion of the recess 114. Cooling water is supplied to the first cooling pipe 121 and the second cooling pipe 122 from a water supply device (not shown).
  • the cooler 12 is composed of the first cooling pipe 121 and the second cooling pipe 122.
  • a roll-shaped aluminum 50 in which a sheet-shaped aluminum is wound is accommodated.
  • the roll-shaped aluminum 50 is obtained by uniformly dispersing granular calcium hydroxide 503 on one sheet-shaped aluminum 501, and superimposing a water-absorbent sheet 502 on the rolled aluminum 501, so as to be wound a plurality of times. It is configured by turning.
  • the water absorbent sheet 502 paper, cloth, nonwoven fabric or the like having a large number of fine holes can be used.
  • the granular calcium hydroxide 503 enters and is held in the holes of the water absorbent sheet 502. Accordingly, the water-absorbent sheet 502 and the calcium hydroxide 503 held by the water-absorbent sheet 502 are interposed between the layers of the roll-shaped aluminum 50.
  • the water absorbent sheet 502 functions as a spacer.
  • the hydrogen generator 10 of the present embodiment is assembled as follows. First, the roll-shaped aluminum 50 is mounted around the concave portion 114 of the lid portion 112, and the lid portion 112 is attached to the container body 111 with the flange 115 overlapped with the flange 113 in this state. Thereby, most of the roll-shaped aluminum 50 is disposed in the annular space 116 in the hydrogen generation container 11 in a vertically placed state. With such a configuration, the rolled aluminum 50 can be easily and reliably accommodated in the annular space 106. Further, the stirring bar 100 is placed in the hydrogen generation vessel 11 as necessary.
  • a bolt (not shown) is inserted into the bolt holes of the flange 115 and the flange 113, and both are fastened and fixed.
  • piping is connected to the gas inlet 13, the gas outlet 14, the safety valve port 15, the water injection port 16, and the attachment port 17, and water is injected into the container body 111 from the water injection port 16.
  • the reaction (1) described above proceeds with water and aluminum, and hydrogen is generated.
  • the generated hydrogen rises through the layers of the roll-like aluminum 50 in a vertically placed state, and travels from the gas outlet 14 to the hydrogen purifier 20 through the pipes 43 to 45.
  • an aluminum oxide or aluminum hydroxide passivated layer is gradually formed on the surface of the aluminum.
  • the above-described reaction (2) by the calcium hydroxide 503 dissolved in water. Prevents the formation of a passive layer. For this reason, hydrogen is continuously generated.
  • the water absorbent sheet 502 is interposed between the layers of the roll aluminum 50, and the granular calcium hydroxide 503 is held in the water absorbent sheet 502. Therefore, water in which calcium hydroxide is dissolved is always present, and the effect of suppressing the formation of the passive layer is improved.
  • the cooler 12 including the first cooling pipe 121 and the second cooling pipe 122 is attached around the annular space 116, so that the annular space 116 is formed. An excessive increase in temperature can be suppressed, and a decrease in reaction rate can be prevented.
  • this invention is not limited to an above-described Example, A suitable change is possible.
  • the hydrogen purifier 20 is provided, but the hydrogen purifier 20 is not required when a degassing membrane that allows hydrogen to pass through the gas outlet 14 provided in the hydrogen generation vessel 11 and blocks moisture is attached. It is.
  • the water-absorbent sheet is used as the spacer, but it is sufficient that the spacer has a function of forming a gap between each layer of rolled aluminum, and the water-absorbent sheet may not be present.
  • the hydrogen generation container is not limited to a cylindrical shape, and may be a rectangular tube shape.
  • a laminate of a plurality of sheet-like aluminums may be arranged in a vertically placed state instead of roll-like aluminum.
  • the hydrogen generating agent accommodated in the hydrogen generating container according to the present invention is not limited to sheet-like aluminum, and granular or massive aluminum may be used.
  • metals such as magnesium, silicon, and zinc can be used.
  • calcium hydroxide, potassium hydroxide, sodium hydroxide, or the like may be used.

Abstract

This hydrogen production device 1 comprises a hydrogen generation apparatus 10), a hydrogen purification apparatus 20 for removing impurity from the hydrogen generated in the hydrogen generation apparatus 10, a hydrogen storage apparatus 30 for storing the hydrogen after the purification, and plumbing 43 to 45 for connecting these apparatuses. The hydrogen generation apparatus 10 is configured from a hydrogen generation vessel 11 and a cooling apparatus 12 for cooling the hydrogen generation vessel 11. On the upper portion of the hydrogen generation vessel 11 are one each of a gas inlet 13, a gas outlet 14, a safety valve port 15, and a water injection port 16, and three mounting ports 17 for mounting probes from a temperature detector 40. When producing hydrogen using the reaction between water and aluminum, the present invention allows hydrogen to be generated continuously over a long time period without decreasing the overall amount of hydrogen produced.

Description

水素製造装置及び水素発生容器Hydrogen production apparatus and hydrogen generation container
　本発明は、燃料電池の燃料等に利用される水素の製造装置及び該製造装置に用いられる水素発生容器に関し、特に、アルミニウムと水の反応を利用した水素製造装置及び水素発生容器に関する。 The present invention relates to a hydrogen production apparatus used as fuel for fuel cells and the like, and a hydrogen generation container used in the production apparatus, and more particularly to a hydrogen production apparatus and a hydrogen generation container using a reaction between aluminum and water.
　燃料電池は、水素と酸素の化学反応により電力を取り出す発電装置の一つであり、既存の発電装置に比べると発電効率が非常に高く、騒音や振動が少ない。また、環境汚染物質をほとんど排出しないことから、ノートパソコン・携帯電話等の携帯機器、家電製品、自動車等の様々な分野での利用が期待されている。このような燃料電池においては、燃料となる水素ガスの製造コストの低減及び生産効率の向上が課題となっている。 A fuel cell is one of the power generation devices that extract electric power through a chemical reaction between hydrogen and oxygen. Compared with existing power generation devices, the power generation efficiency is very high, and noise and vibration are low. In addition, since it emits almost no environmental pollutants, it is expected to be used in various fields such as portable devices such as notebook computers and mobile phones, home appliances, and automobiles. In such a fuel cell, the reduction of the manufacturing cost of hydrogen gas used as a fuel and the improvement of production efficiency are problems.
　例えば特許文献１には、粒子状のアルミニウムと水酸化カルシウムを含む水素発生剤を水と接触させることにより水素ガスを製造する方法が開示されている。この方法では、比較的安価な金属アルミニウムを水素発生剤として用いるため、製造コストを低減することができる。また、アルミニウムと水の反応により粒子表面に形成される不溶層（アルミ酸化物又はアルミ水酸化物の不動態層）を水酸化カルシウムによって可溶化して未反応のアルミニウム金属面を形成することにより、水素の発生効率を高めている。 For example, Patent Document 1 discloses a method for producing hydrogen gas by bringing a hydrogen generator containing particulate aluminum and calcium hydroxide into contact with water. In this method, since relatively inexpensive metal aluminum is used as the hydrogen generating agent, the manufacturing cost can be reduced. In addition, an insoluble layer (aluminum oxide or a passive layer of aluminum hydroxide) formed on the particle surface by the reaction of aluminum and water is solubilized with calcium hydroxide to form an unreacted aluminum metal surface. , Increase the efficiency of hydrogen generation.
特開2013-006734号公報JP 2013-006734 A
　上記方法では、不溶層の形成を抑えて水素ガスの総発生量を増加させるためにはアルミニウムの粒径を小さくして比表面積（表面積／体積）を大きくすることが望ましい。ところが、アルミニウムの粒径を小さくすると水との反応が急激に進行するため、短時間で反応が終了してしましまう。しかも、日本では、粒径が150μm以下のアルミニウム粉末は消防法において危険物（第一種可燃性固体（危険等級II））として指定されており（危険物の規制に関する政令第１条の１１、別表第三）、取り扱い量によっては届出が必要となるという問題があった。 In the above method, in order to suppress the formation of an insoluble layer and increase the total generation amount of hydrogen gas, it is desirable to reduce the particle size of aluminum and increase the specific surface area (surface area / volume). However, when the particle size of aluminum is reduced, the reaction with water proceeds rapidly, and the reaction is completed in a short time. Moreover, in Japan, aluminum powder with a particle size of 150 μm or less is designated as a dangerous substance (Class 1 flammable solid (hazardous grade II)) by the Fire Service Act (Decree Article 11-11 of the Regulation on Dangerous Goods) There is a problem that notification is necessary depending on the amount handled.
　本発明が解決しようとする課題は、水とアルミニウムの反応を利用して水素を製造する際に、水素の総発生量を低下させることなく長時間継続して水素を発生させることができ、しかも、水素を発生させるための材料の取り扱いが容易な水素製造装置及び水素発生容器を提供することである。 The problem to be solved by the present invention is that when hydrogen is produced using the reaction between water and aluminum, hydrogen can be generated continuously for a long time without reducing the total amount of generated hydrogen, An object of the present invention is to provide a hydrogen production apparatus and a hydrogen generation vessel in which handling of materials for generating hydrogen is easy.
　本発明者は、上記課題を解決するため鋭意検討を重ねた結果、日本の消防法において危険物に指定されていないシート状のアルミニウムを水素発生材料として用いることにより、水素の発生反応を長時間持続させることができること、さらに、シート状のアルミニウムと、水及び水酸化カルシウムとをいかに効率よく接触させるかが、水素の発生効率の向上に重要であることを見出した。本発明は、このような新たな知見に基づき成されたものである。 As a result of intensive studies in order to solve the above problems, the present inventor has used a sheet-like aluminum not designated as a hazardous material in the Japanese Fire Service Act as a hydrogen generating material, thereby allowing a long period of hydrogen generation reaction. It has been found that it is important to improve the hydrogen generation efficiency that it can be sustained, and how efficiently the sheet-like aluminum is brought into contact with water and calcium hydroxide. The present invention has been made based on such new findings.
　すなわち、上記課題を解決するために成された本発明に係る水素製造装置は、
　水と金属アルミニウムの反応を利用して水素ガスを製造する装置であって、
　a) 筒状の外周壁部と、該外周壁部の内側に配置された、該外周壁部との間に環状空間を形成する筒状の内周壁部とを備えた水素発生容器と、
　b) 前記環状空間に縦置き状態で収容された１又は複数枚のシート状アルミニウムと、
　c) 前記水素発生容器内に収容された粒状の水酸化カルシウムと、
　d) 前記水素発生容器に設けられた該水素発生容器内に水を供給するための水供給口と、
　e) 前記環状空間の上部に位置するように前記水素発生容器に設けられた水素取出口と
　を備えることを特徴とする。 That is, the hydrogen production apparatus according to the present invention, which has been made to solve the above problems,
An apparatus for producing hydrogen gas using a reaction between water and metal aluminum,
a) a hydrogen generation container including a cylindrical outer peripheral wall portion and a cylindrical inner peripheral wall portion that is disposed inside the outer peripheral wall portion and forms an annular space between the outer peripheral wall portion;
b) one or more sheet-like aluminum accommodated in the annular space in a vertically placed state;
c) granular calcium hydroxide contained in the hydrogen generation vessel;
d) a water supply port for supplying water into the hydrogen generation container provided in the hydrogen generation container;
e) a hydrogen outlet provided in the hydrogen generation container so as to be positioned above the annular space.
　本発明の水素製造装置では、環状空間にシート状アルミニウムを縦置き状態で配置した水素発生容器内に水及び水酸化カルシウムを収容すると、水酸化カルシウムの一部が水に溶解する。このとき、水とアルミニウムの以下の反応（１）により水素（ガス）が発生する。
　２Ａｌ　＋　６Ｈ２Ｏ　→　２Ａｌ（ＯＨ）３　＋　３Ｈ２　　（１）
　ここで「縦置き状態」とは、シート状アルミニウムが水平面とほぼ垂直な状態をいう。水素は水に溶けにくく、且つ、空気よりも軽いため、水とシート状アルミニウムの反応により発生した水素は水素発生容器内の水中を上昇し、水素取出口から水素発生容器の外部に取り出される。このとき、シート状アルミニウムが縦置き状態に配置されているため、水素はシート状アルミニウムの表面に沿って上昇し、シート状アルミニウムに邪魔されることがない。また、シート状アルミニウムの表面付近を水素が通過することにより、シート状アルミニウムと水素発生容器の壁面との間や、複数のシート状アルミニウムの間に間隙が形成され、水が流通し易くなるため、アルミニウムと水の反応効率が向上する。 In the hydrogen production apparatus of the present invention, when water and calcium hydroxide are accommodated in a hydrogen generation container in which sheet-like aluminum is placed in a vertical state in an annular space, a part of calcium hydroxide is dissolved in water. At this time, hydrogen (gas) is generated by the following reaction (1) between water and aluminum.
2Al + 6H 2 O → 2Al (OH) 3 + 3H 2 (1)
Here, the “longitudinal state” refers to a state in which the sheet-like aluminum is substantially perpendicular to the horizontal plane. Since hydrogen is hardly dissolved in water and lighter than air, hydrogen generated by the reaction between water and sheet-like aluminum rises in the water in the hydrogen generation container and is taken out from the hydrogen outlet to the outside of the hydrogen generation container. At this time, since the sheet-like aluminum is arranged vertically, hydrogen rises along the surface of the sheet-like aluminum and is not obstructed by the sheet-like aluminum. In addition, since hydrogen passes near the surface of the sheet-like aluminum, gaps are formed between the sheet-like aluminum and the wall surface of the hydrogen generation container or between the plurality of sheet-like aluminum, so that water can easily flow. , The reaction efficiency of aluminum and water is improved.
　さらに、シート状アルミニウムと水が反応する空間を環状空間にしたため、反応熱を環状空間の外周壁部及び内周壁部の両方から放出することができ、放熱効果が向上する。このため、反応空間が過度に温度上昇することを防止することができ、反応速度の低下を抑えることができる。 Furthermore, since the space where the sheet-like aluminum and water react is an annular space, the reaction heat can be released from both the outer peripheral wall portion and the inner peripheral wall portion of the annular space, and the heat dissipation effect is improved. For this reason, it is possible to prevent the temperature of the reaction space from rising excessively, and to suppress a decrease in the reaction rate.
　水とアルミニウムの反応が進行すると、アルミニウムの表面にアルミ酸化物又はアルミ水酸化物の不動態層が徐々に形成され、反応速度が低下する。これに対して、本発明では、水素発生容器内に水酸化カルシウムを収容したため、水に溶解した水酸化カルシウムによる以下の反応（２）により不動態層の形成を妨げることができる。このため、継続的に水素を発生させることができ、水素発生効率が向上する。
　２Ａｌ（ＯＨ）３　＋　３Ｃａ（ＯＨ）２　→　Ｃａ３Ａｌ２（ＯＨ）１２　（２） As the reaction between water and aluminum proceeds, an aluminum oxide or aluminum hydroxide passive layer is gradually formed on the surface of the aluminum, and the reaction rate decreases. On the other hand, in this invention, since calcium hydroxide was accommodated in the hydrogen generation container, formation of a passive layer can be prevented by the following reaction (2) with calcium hydroxide dissolved in water. For this reason, hydrogen can be continuously generated, and the hydrogen generation efficiency is improved.
2Al (OH) 3 + 3Ca (OH) 2 → Ca 3 Al 2 (OH) 12 (2)
　上記水素製造装置においては、前記水素発生容器内の圧力を１MPa未満に維持するための圧力維持手段を備えることが好ましい。このような構成によれば、水素製造装置の設置の際や水素製造装置を稼働する際等に日本の高圧ガス保安法のような法令による規制を受けなくても済むため、取り扱いが容易になる。 In the hydrogen production apparatus, it is preferable to include a pressure maintaining means for maintaining the pressure in the hydrogen generation container below 1 MPa. According to such a configuration, it is not necessary to be regulated by laws and regulations such as the Japanese High Pressure Gas Safety Act when installing the hydrogen production apparatus or operating the hydrogen production apparatus, so that handling becomes easy. .
　また、前記内周壁部を取り囲むように、１枚の前記シート状アルミニウムを複数回巻回したロール状アルミニウムを前記環状空間に収容すると良い。このような構成によると、内周壁部によってシート状アルミニウム（ロール状アルミニウム）を保持することができる。 Also, roll-shaped aluminum obtained by winding a single sheet-shaped aluminum a plurality of times so as to surround the inner peripheral wall portion may be accommodated in the annular space. According to such a structure, sheet-like aluminum (roll-like aluminum) can be hold | maintained by an inner peripheral wall part.
　上記構成においては、前記ロール状アルミニウムの各層の間にスペーサが介装されていると良い。このような構成によると、ロール状アルミニウムの各層間に確実に間隙を形成することができるため、アルミニウムと水との反応効率を一層向上することができる。また、アルミニウムと水との反応により発生した水素の通路をロール状アルミニウムの各層間に確保することができるという効果も奏する。 In the above configuration, a spacer may be interposed between the layers of the rolled aluminum. According to such a configuration, a gap can be surely formed between each layer of rolled aluminum, so that the reaction efficiency between aluminum and water can be further improved. In addition, there is an effect that hydrogen passages generated by the reaction between aluminum and water can be secured between the layers of roll aluminum.
　さらに、前記スペーサを吸水性材料から構成し、該スペーサに前記粒状の水酸化カルシウムを保持するようにすると、ロール状アルミニウムの各層間に水酸化カルシウムを含む水を存在させることができる。このため、アルミ酸化物又はアルミ水酸化物の不動態層がアルミニウムの表面に形成されることを一層防止できる。 Furthermore, when the spacer is made of a water-absorbing material and the granular calcium hydroxide is held in the spacer, water containing calcium hydroxide can be present between the respective layers of the rolled aluminum. For this reason, it can further prevent that the passive layer of aluminum oxide or aluminum hydroxide is formed on the surface of aluminum.
　ロール状アルミニウムの各層の間にスペーサを介在させる構成は、例えばシート状アルミニウムと略大きさのシート状スペーサを用意し、両者を重ね合わせて複数回巻回することにより実現することができる。シート状スペーサとしては、吸水性に優れた紙や布、不織布等を用いることができる。また、綿（ワタ）やスポンジ等をスペーサとして用いても良い。 The configuration in which a spacer is interposed between each layer of roll-shaped aluminum can be realized, for example, by preparing sheet-shaped aluminum and a sheet-shaped spacer of approximately the same size, and superimposing both and winding them a plurality of times. As the sheet-like spacer, paper, cloth, nonwoven fabric or the like excellent in water absorption can be used. Cotton, sponge, or the like may be used as the spacer.
　本発明に係る水素製造装置においては、前記水素発生容器を、上部開口を有する有底円筒状の容器本体と、該容器本体の上部開口を塞ぐ蓋部であって、前記容器本体内に入り込む有底円筒状の凹部を有する蓋部とから構成すると良い。この構成では、前記容器本体の側壁部が前記外周壁部を構成し、前記蓋部の凹部の側壁部が前記内周壁部を構成する。
　上記構成によれば、蓋部の凹部の周りにロール状アルミニウムを装着した後、該蓋部で容器本体の上部開口を塞ぐことにより、簡単に水素発生容器を組み立てることができる。 In the hydrogen production apparatus according to the present invention, the hydrogen generation container includes a bottomed cylindrical container body having an upper opening, and a lid that closes the upper opening of the container body, and enters the container body. It is good to comprise from the cover part which has a bottom cylindrical recessed part. In this structure, the side wall part of the said container main body comprises the said outer peripheral wall part, and the side wall part of the recessed part of the said cover part comprises the said inner peripheral wall part.
According to the said structure, after mounting roll-shaped aluminum around the recessed part of a cover part, a hydrogen generation container can be easily assembled by plugging the upper opening of a container main body with this cover part.
　また、前記外周壁部及び前記内周壁部の少なくとも一方を冷却するための冷却装置を設けると、前記外周壁部及び／又は前記内周壁部から効率よく放熱することができる。 Further, when a cooling device for cooling at least one of the outer peripheral wall portion and the inner peripheral wall portion is provided, heat can be efficiently radiated from the outer peripheral wall portion and / or the inner peripheral wall portion.
　上記冷却装置は、前記外周壁部の外面に沿って巻装された、冷却水が流通する第１水冷管と、前記内周壁部の外面に沿って巻装された、冷却水が流通する第２水冷管とから構成することができる。 The cooling device includes a first water-cooled pipe wound along the outer surface of the outer peripheral wall portion and circulating the cooling water, and a first water-cooled pipe wound along the outer surface of the inner peripheral wall portion. It can be composed of two water-cooled tubes.
　さらに、上記課題を解決するために成された本発明に係る水素発生容器は、筒状の外周壁部と、該外周壁部の内側に配置された、該外周壁部との間に環状空間を形成する筒状の内周壁部とを備え、
　前記環状空間に水及び水素発生剤を収容し、前記水と前記水素発生剤との反応により水素を発生させることを特徴とする。 Furthermore, a hydrogen generation container according to the present invention, which has been made to solve the above problems, has an annular space between a cylindrical outer peripheral wall portion and the outer peripheral wall portion arranged inside the outer peripheral wall portion. A cylindrical inner peripheral wall part forming
Water and a hydrogen generating agent are accommodated in the annular space, and hydrogen is generated by a reaction between the water and the hydrogen generating agent.
　本発明では、アルミニウムと水の反応を利用した水素製造装置において従来用いられていた粒状のアルミニウムに代えてシート状アルミニウムを用いることにより、長時間継続して水素ガスを発生させることができる。しかも、シート状アルミニウムの収容に適した形状の水素発生容器、すなわち、筒状の外周壁部と、該外周壁部の内側に配置された、該外周壁部との間に環状空間を形成する筒状の内周壁部とを備えた水素発生容器を用い、その環状空間に縦置き状態で１又は複数枚のシート状アルミニウム収容するようにしたため、水とアルミニウムの反応効率、すなわち、水素発生効率を向上することができる。 In the present invention, hydrogen gas can be generated continuously for a long time by using sheet-like aluminum in place of granular aluminum conventionally used in a hydrogen production apparatus utilizing the reaction between aluminum and water. In addition, a hydrogen generation container having a shape suitable for accommodating sheet-like aluminum, that is, an annular space is formed between the cylindrical outer peripheral wall portion and the outer peripheral wall portion disposed inside the outer peripheral wall portion. Since a hydrogen generation container having a cylindrical inner peripheral wall portion is used and one or a plurality of sheet-like aluminum is accommodated vertically in the annular space, the reaction efficiency of water and aluminum, that is, the hydrogen generation efficiency Can be improved.
本発明に係る水素製造装置の一実施例を示す概略的な全体構成図。BRIEF DESCRIPTION OF THE DRAWINGS The schematic whole block diagram which shows one Example of the hydrogen production apparatus based on this invention. 水素発生容器の縦断側面図（ａ）、及び上面図（ｂ）。The vertical side view (a) and top view (b) of a hydrogen generation container. ロール状アルミニウム及び水を収容した状態の水素発生容器の縦断側面図。The vertical side view of the hydrogen generation container of the state which accommodated roll-shaped aluminum and water. シート状アルミニウムの作製方法の説明図。Explanatory drawing of the preparation methods of sheet-like aluminum.
　以下、本発明に係る水素製造装置の一実施例について図面を用いて説明する。
　図１は、本実施例の水素製造装置の全体構成を示す概略図である。水素製造装置１は、水素発生器１０と、該水素発生器１０で発生した水素から不純物を除去するための水素精製器２０と、精製後の水素を貯蔵する水素貯蔵器３０と、これらを繋ぐ配管とから構成されている。 Hereinafter, an embodiment of a hydrogen production apparatus according to the present invention will be described with reference to the drawings.
FIG. 1 is a schematic diagram showing the overall configuration of the hydrogen production apparatus of this example. The hydrogen production apparatus 1 connects the hydrogen generator 10, the hydrogen purifier 20 for removing impurities from the hydrogen generated in the hydrogen generator 10, and the hydrogen reservoir 30 for storing the purified hydrogen. It consists of piping.
　水素発生器１０は、水素発生容器１１と該水素発生容器１１を冷却するための冷却器１２とから構成されている。水素発生容器１１の上部には、ガス出口１３、安全弁口１４（手動式）、安全弁口（圧力感知式）１５、及び注水口１６がそれぞれ１個ずつ、及び温度検出器４０のプローブを取り付けるための取付口１７が１個設けられている。水素取出口であるガス出口１３には、配管４１、４５を介して水素精製器２０が接続されている。また、水素発生容器１１の下部には排水口１８が設けられている。水素発生容器１１内の圧力はガス出口１３より圧力計４２を介してモニタリングされている。水素発生容器１１の内圧が１MPaを超えると圧力計４２からの信号を受けてバルブ４２ａが開放され、排気される。水素発生容器１１及び冷却器１２の構成については後述する。 The hydrogen generator 10 includes a hydrogen generation container 11 and a cooler 12 for cooling the hydrogen generation container 11. A gas outlet 13, a safety valve port 14 (manual type), a safety valve port (pressure sensing type) 15, and a water injection port 16 are respectively provided on the upper part of the hydrogen generation container 11, and a probe for the temperature detector 40 is attached. One mounting port 17 is provided. A hydrogen purifier 20 is connected to the gas outlet 13, which is a hydrogen outlet, via pipes 41 and 45. A drain port 18 is provided at the lower part of the hydrogen generation container 11. The pressure in the hydrogen generation container 11 is monitored from the gas outlet 13 via the pressure gauge 42. When the internal pressure of the hydrogen generating container 11 exceeds 1 MPa, a signal from the pressure gauge 42 is received and the valve 42a is opened and exhausted. The configuration of the hydrogen generation container 11 and the cooler 12 will be described later.
　水素精製器２０は、下端面に入口部２１、上端面に出口部２２を有する筒状容器２３の内部にゼオライト（商品名：モレキュラーシーブ）やシリカゲル等の乾燥剤（図示せず）を充填して構成されている。水素精製器２０の入口部２１には前記配管４５が接続されており、出口部２２には配管４６を介して水素貯蔵器３０が接続されている。配管４５にはガス調節弁４７が取り付けられており、水素発生容器１１の内圧が１MPaを超えないように水素発生器１０から水素精製器２０に向かう水素ガスの流量を調節する。このように、本実施例では、圧力計４２とバルブ４２ａ、およびガス調節弁４７により水素発生容器１１の内圧が１MPa未満に維持されており、水素製造装置１の設置の際や水素製造装置１を稼働する際等に高圧ガス保安法による規制を受けなくても済む。このため、水素製造装置１の取り扱いが容易になる。また、筒状容器２３の下端面には、該筒状容器２３内に溜まった水分を排出するためのドレン管２４が接続されている。 The hydrogen purifier 20 is filled with a desiccant (not shown) such as zeolite (trade name: molecular sieve) or silica gel in a cylindrical container 23 having an inlet 21 at the lower end and an outlet 22 at the upper end. Configured. The pipe 45 is connected to the inlet 21 of the hydrogen purifier 20, and the hydrogen reservoir 30 is connected to the outlet 22 via a pipe 46. A gas control valve 47 is attached to the pipe 45, and the flow rate of hydrogen gas from the hydrogen generator 10 toward the hydrogen purifier 20 is adjusted so that the internal pressure of the hydrogen generation vessel 11 does not exceed 1 MPa. As described above, in this embodiment, the internal pressure of the hydrogen generating container 11 is maintained at less than 1 MPa by the pressure gauge 42, the valve 42a, and the gas regulating valve 47, so that the hydrogen producing apparatus 1 or the hydrogen producing apparatus 1 is installed. It is not necessary to be regulated by the High Pressure Gas Safety Law when operating For this reason, handling of the hydrogen production apparatus 1 becomes easy. In addition, a drain pipe 24 for discharging water accumulated in the cylindrical container 23 is connected to the lower end surface of the cylindrical container 23.
　水素貯蔵器３０は、水素導入口３１を備えるカートリッジ式の水素貯蔵容器３２と、水素導入口３１に着脱可能に接続される配管３３と、該配管３３に設けられた水素流量をモニタリングするマスフローメーター３４とから成る。水素貯蔵容器３２の内部には水素吸蔵合金（図示せず）が収容されている。また、配管３３は前記配管４６に接続されている。 The hydrogen reservoir 30 includes a cartridge-type hydrogen storage container 32 having a hydrogen inlet 31, a pipe 33 that is detachably connected to the hydrogen inlet 31, and a mass flow meter that monitors the hydrogen flow rate provided in the pipe 33. 34. A hydrogen storage alloy (not shown) is accommodated in the hydrogen storage container 32. The pipe 33 is connected to the pipe 46.
　水素貯蔵容器３２に水素を貯蔵するときは、配管３３を水素導入口３１に接続する。これにより、水素精製器２０で水分が除去された水素ガスが配管４６および配管３３を経て水素貯蔵容器３２内に導入され、水素吸蔵合金に吸収される。水素の吸収が完了した水素貯蔵容器３２は、水素導入口３１から配管３３を取り外し、該導入口３１を封止することにより水素源として保管される。また、配管３３に別の新たな水素貯蔵容器３２の水素導入口３１を接続することにより、水素発生器１０で発生した水素を再び水素貯蔵容器３２内に貯蔵することができる。水素が貯蔵された水素貯蔵容器３２は、例えば燃料電池ユニットに接続することにより、水素吸蔵合金に吸収された水素を燃料電池の燃料として供給することができる。 When storing hydrogen in the hydrogen storage container 32, the pipe 33 is connected to the hydrogen inlet 31. Thereby, the hydrogen gas from which moisture has been removed by the hydrogen purifier 20 is introduced into the hydrogen storage container 32 through the pipe 46 and the pipe 33 and is absorbed by the hydrogen storage alloy. The hydrogen storage container 32 that has completed the absorption of hydrogen is stored as a hydrogen source by removing the pipe 33 from the hydrogen inlet 31 and sealing the inlet 31. Further, by connecting the hydrogen inlet 31 of another new hydrogen storage container 32 to the pipe 33, the hydrogen generated in the hydrogen generator 10 can be stored again in the hydrogen storage container 32. The hydrogen storage container 32 in which hydrogen is stored can supply hydrogen absorbed in the hydrogen storage alloy as fuel for the fuel cell, for example, by connecting to the fuel cell unit.
　この場合、水素貯蔵容器３２を冷却したり加熱したりしなくても水素の吸放出が可能な水素吸蔵合金を用いることが好ましい。また、水素の吸蔵時と同程度の温度条件下で、水素吸蔵時と同じ圧力の水素を放出できるような水素吸蔵合金を用いると、水素放出時に電力を消費しなくても済み、使い勝手が良い。このような水素貯蔵容器３２としては、例えば株式会社ワイエムシィ製の「水素吸蔵合金キャニスター」が挙げられる。 In this case, it is preferable to use a hydrogen storage alloy capable of absorbing and releasing hydrogen without cooling or heating the hydrogen storage container 32. Also, using a hydrogen storage alloy that can release hydrogen at the same pressure as during hydrogen storage under the same temperature conditions as during storage of hydrogen, it is not necessary to consume power when releasing hydrogen, which is easy to use. . Examples of such a hydrogen storage container 32 include “hydrogen storage alloy canister” manufactured by YMC Co., Ltd.
　なお、符号は付していないが、配管４１、４３～４６並びにドレン管２４の適宜の箇所には、上記の他にそれぞれプラグ弁、圧力調節弁、流量調節弁、安全弁等が取り付けられている。 In addition, although not indicated, a plug valve, a pressure regulating valve, a flow regulating valve, a safety valve, etc. are attached to appropriate portions of the pipes 41, 43 to 46 and the drain pipe 24 in addition to the above. .
　次に、図１ないし図３を参照して水素発生容器１１及び冷却器１２の構造について説明する。水素発生容器１１は、円筒状の容器本体１１１と、該容器本体１１１の上部開口を塞ぐ蓋部１１２とから成る。容器本体１１１の上部外周には円環状のフランジ１１３が取り付けられており、容器本体１１１の下部に前記排水口１８が設けられている。 Next, the structure of the hydrogen generation vessel 11 and the cooler 12 will be described with reference to FIGS. 1 to 3. The hydrogen generation container 11 includes a cylindrical container body 111 and a lid portion 112 that closes an upper opening of the container body 111. An annular flange 113 is attached to the upper outer periphery of the container main body 111, and the drain port 18 is provided at the lower part of the container main body 111.
　蓋部１１２は、半球面状の底面を有する円筒状の凹部１１４と該凹部１１４の上部外周に設けられた円環状のフランジ１１５とを有している。フランジ１１５の外径は容器本体１１１のフランジ１１３と外径とほぼ同じに設計され、フランジ１１５の内径（すなわち凹部１１４の直径）はフランジ１１３の内径（すなわち容器本体１１１の直径）よりもひと回り小さく設計されている。そして、フランジ１１３の上にフランジ１１５を重ねて容器本体１１１の上部開口を蓋部１１２で閉塞したとき、凹部１１４が容器本体１１１の内側に入り込み、且つ、凹部１１４と容器本体１１１の側壁部との間に円環状の空間が形成され、凹部１１４と容器本体１１１の底面との間に凹状の空間が形成されるように、凹部１１４の大きさが設定されている。以下の説明では、凹部１１４と容器本体１１１の側壁部との間の空間を環状空間１１６という。なお、フランジ１１３の上にフランジ１１５を重ねたとき、フランジ１１５のうち環状空間１１６の上部に位置する箇所に、上述のガス入口１３、ガス出口１４、安全弁口１５、及び注水口１６、取付口１７が設けられている。また、本実施例では凹部１１４の下面は半球面状にしたが、容器本体１１１の底面と同様の平坦面状にしても良い。 The lid portion 112 has a cylindrical concave portion 114 having a hemispherical bottom surface and an annular flange 115 provided on the upper outer periphery of the concave portion 114. The outer diameter of the flange 115 is designed to be almost the same as the outer diameter of the flange 113 of the container body 111, and the inner diameter of the flange 115 (that is, the diameter of the recess 114) is slightly smaller than the inner diameter of the flange 113 (that is, the diameter of the container body 111). Designed. Then, when the flange 115 is overlapped on the flange 113 and the upper opening of the container body 111 is closed with the lid 112, the recess 114 enters the inside of the container body 111, and the recess 114 and the side wall of the container body 111 The size of the concave portion 114 is set so that an annular space is formed between the concave portions 114 and the concave space is formed between the concave portion 114 and the bottom surface of the container body 111. In the following description, the space between the concave portion 114 and the side wall portion of the container main body 111 is referred to as an annular space 116. When the flange 115 is overlaid on the flange 113, the gas inlet 13, gas outlet 14, safety valve port 15, water injection port 16, and mounting port described above are located in the upper portion of the annular space 116 in the flange 115. 17 is provided. In the present embodiment, the lower surface of the recess 114 has a hemispherical shape, but may be a flat surface similar to the bottom surface of the container body 111.
　容器本体１１１の側壁部の外周面及び凹部１１４の側壁部の内周面には、それぞれコイル状の第１冷却管１２１及びコイル状の第２冷却管１２２がそれぞれ巻装されている。第１冷却管１２１及び第２冷却管１２２にはそれぞれ図示しない給水装置から冷却水が供給される。第１冷却管１２１及び第２冷却管１２２から冷却器１２が構成されている。 The coiled first cooling pipe 121 and the coiled second cooling pipe 122 are respectively wound around the outer peripheral surface of the side wall portion of the container body 111 and the inner peripheral surface of the side wall portion of the recess 114. Cooling water is supplied to the first cooling pipe 121 and the second cooling pipe 122 from a water supply device (not shown). The cooler 12 is composed of the first cooling pipe 121 and the second cooling pipe 122.
　また、水素発生容器１１内には、シート状アルミニウムを巻回したロール状アルミニウム５０が収容されている。図４に示すように、ロール状アルミニウム５０は、１枚のシート状アルミニウム５０１の上に粒状の水酸化カルシウム５０３を万遍なく分散させ、その上に吸水性シート５０２を重ね合わせて複数回巻回することにより構成されている。吸水性シート５０２としては、多数の微細な孔を有する紙や布、不織布等を用いることができる。このような吸水性シート５０２を用いることにより、粒状の水酸化カルシウム５０３は吸水性シート５０２の孔に入り込み、保持される。従って、ロール状アルミニウム５０の各層の間には吸水性シート５０２及びこれに保持された水酸化カルシウム５０３が介在する。吸水性シート５０２はスペーサとして機能する。 Further, in the hydrogen generation container 11, a roll-shaped aluminum 50 in which a sheet-shaped aluminum is wound is accommodated. As shown in FIG. 4, the roll-shaped aluminum 50 is obtained by uniformly dispersing granular calcium hydroxide 503 on one sheet-shaped aluminum 501, and superimposing a water-absorbent sheet 502 on the rolled aluminum 501, so as to be wound a plurality of times. It is configured by turning. As the water absorbent sheet 502, paper, cloth, nonwoven fabric or the like having a large number of fine holes can be used. By using such a water absorbent sheet 502, the granular calcium hydroxide 503 enters and is held in the holes of the water absorbent sheet 502. Accordingly, the water-absorbent sheet 502 and the calcium hydroxide 503 held by the water-absorbent sheet 502 are interposed between the layers of the roll-shaped aluminum 50. The water absorbent sheet 502 functions as a spacer.
　本実施例の水素発生器１０は以下のようにして組み立てられる。
　まず、ロール状アルミニウム５０を蓋部１１２の凹部１１４の周りに装着し、この状態でフランジ１１５をフランジ１１３に重ね合わせて蓋部１１２を容器本体１１１に取り付ける。これにより、ロール状アルミニウム５０の大部分が水素発生容器１１内の環状空間１１６に縦置き状態で配置される。このような構成により、ロール状アルミニウム５０を簡単且つ確実に環状空間１０６に収容することができる。また、必要に応じて水素発生容器１１内に撹拌子１００を入れる。
　続いて、フランジ１１５とフランジ１１３のボルト穴にボルト（図示せず）を挿通し、両者を締め付け固定する。その後、ガス入口１３、ガス出口１４、安全弁口１５、及び注水口１６、取付口１７に配管を接続し、注水口１６から容器本体１１１内に水を注入する。 The hydrogen generator 10 of the present embodiment is assembled as follows.
First, the roll-shaped aluminum 50 is mounted around the concave portion 114 of the lid portion 112, and the lid portion 112 is attached to the container body 111 with the flange 115 overlapped with the flange 113 in this state. Thereby, most of the roll-shaped aluminum 50 is disposed in the annular space 116 in the hydrogen generation container 11 in a vertically placed state. With such a configuration, the rolled aluminum 50 can be easily and reliably accommodated in the annular space 106. Further, the stirring bar 100 is placed in the hydrogen generation vessel 11 as necessary.
Subsequently, a bolt (not shown) is inserted into the bolt holes of the flange 115 and the flange 113, and both are fastened and fixed. Thereafter, piping is connected to the gas inlet 13, the gas outlet 14, the safety valve port 15, the water injection port 16, and the attachment port 17, and water is injected into the container body 111 from the water injection port 16.
　上記のように組み立てられた水素発生器１０では、水とアルミニウムによって上述した反応（１）が進行し、水素が発生する。発生した水素は縦置き状態のロール状アルミニウム５０の各層の間を通って上昇し、ガス出口１４から配管４３～４５を通って水素精製器２０に向かう。また、水とアルミニウムの反応が進行すると、アルミニウムの表面にアルミ酸化物又はアルミ水酸化物の不動態層が徐々に形成されるが、水に溶解した水酸化カルシウム５０３による上述した反応（２）によって、不動態層の形成が妨げられる。このため、継続的に水素が発生する。特に、本実施例では、ロール状アルミニウム５０の各層の間に吸水性シート５０２を介装し、この吸水性シート５０２に粒状の水酸化カルシウム５０３を保持させたため、ロール状アルミニウム５０の各層の近傍に水酸化カルシウムが溶解した水が常時存在することになり、不動態層の形成抑制効果が向上する。 In the hydrogen generator 10 assembled as described above, the reaction (1) described above proceeds with water and aluminum, and hydrogen is generated. The generated hydrogen rises through the layers of the roll-like aluminum 50 in a vertically placed state, and travels from the gas outlet 14 to the hydrogen purifier 20 through the pipes 43 to 45. As the reaction between water and aluminum proceeds, an aluminum oxide or aluminum hydroxide passivated layer is gradually formed on the surface of the aluminum. The above-described reaction (2) by the calcium hydroxide 503 dissolved in water. Prevents the formation of a passive layer. For this reason, hydrogen is continuously generated. In particular, in this embodiment, the water absorbent sheet 502 is interposed between the layers of the roll aluminum 50, and the granular calcium hydroxide 503 is held in the water absorbent sheet 502. Therefore, water in which calcium hydroxide is dissolved is always present, and the effect of suppressing the formation of the passive layer is improved.
　さらに、水とアルミニウムの反応に伴い熱が発生するが、本実施例では、環状空間１１６の周りに第１冷却管１２１及び第２冷却管１２２から成る冷却器１２を取り付けたため、環状空間１１６が過度に温度上昇することが抑えられ、反応速度の低下を防止できる。 Furthermore, although heat is generated with the reaction between water and aluminum, in this embodiment, the cooler 12 including the first cooling pipe 121 and the second cooling pipe 122 is attached around the annular space 116, so that the annular space 116 is formed. An excessive increase in temperature can be suppressed, and a decrease in reaction rate can be prevented.
　なお、本発明は上記した実施例に限定されるものではなく、適宜の変更が可能である。
　例えば、上記実施例では水素精製器２０を設けたが、水素発生容器１１に設けられたガス出口１４に水素を透過させ、水分を遮断する脱気膜を取り付けた場合は水素精製器２０は不要である。 In addition, this invention is not limited to an above-described Example, A suitable change is possible.
For example, in the above embodiment, the hydrogen purifier 20 is provided, but the hydrogen purifier 20 is not required when a degassing membrane that allows hydrogen to pass through the gas outlet 14 provided in the hydrogen generation vessel 11 and blocks moisture is attached. It is.
　上記した実施例では、スペーサとして吸水性シートを用いたが、ロール状アルミニウムの各層の間に間隙を形成する機能を有すれば良く、吸水性を有していなくてもよい。 In the above-described embodiments, the water-absorbent sheet is used as the spacer, but it is sufficient that the spacer has a function of forming a gap between each layer of rolled aluminum, and the water-absorbent sheet may not be present.
　水素発生容器は円筒状に限らず、角筒状でも良い。角筒状の水素発生容器の場合、環状空間にはロール状アルミニウムではなく、複数枚のシート状アルミニウムを積層したものを縦置き状態に配置しても良い。 The hydrogen generation container is not limited to a cylindrical shape, and may be a rectangular tube shape. In the case of a rectangular tube-shaped hydrogen generation container, in the annular space, a laminate of a plurality of sheet-like aluminums may be arranged in a vertically placed state instead of roll-like aluminum.
　また、本発明に係る水素発生容器に収容される水素発生剤はシート状アルミニウムに限らず、粒状や塊状のアルミニウムを用いても良い。また、アルミニウムに限らず、マグネシウムやシリコン、亜鉛等の金属を用いることができる。さらに、水酸化カルシウムの他、水酸化カリウム、水酸化ナトリウム等を用いても良い。 Further, the hydrogen generating agent accommodated in the hydrogen generating container according to the present invention is not limited to sheet-like aluminum, and granular or massive aluminum may be used. In addition to aluminum, metals such as magnesium, silicon, and zinc can be used. Furthermore, in addition to calcium hydroxide, potassium hydroxide, sodium hydroxide, or the like may be used.
１…水素製造装置
１０…水素発生器
１１…水素発生容器
　１１１…容器本体
　１１２…蓋部
　１１３、１１５…フランジ
　１１４…凹部
　１１６…環状空間
１２…冷却器
１４…ガス出口（水素取出口）
１６…注水口
２０…水素精製器
３０…水素貯蔵器
３２…水素貯蔵容器
４２…圧力計（圧力維持手段）
　４２ａ…バルブ（圧力維持手段）
４７…ガス調節弁（圧力維持手段）
５０…ロール状アルミニウム
　５０１…シート状アルミニウム
　５０２…吸水性シート
　５０３…粒状の水酸化カルシウム DESCRIPTION OF SYMBOLS 1 ... Hydrogen production apparatus 10 ... Hydrogen generator 11 ... Hydrogen generation container 111 ... Container main body 112 ... Lid part 113, 115 ... Flange 114 ... Recessed part 116 ... Annular space 12 ... Cooler 14 ... Gas outlet (hydrogen outlet)
16 ... Water injection port 20 ... Hydrogen purifier 30 ... Hydrogen reservoir 32 ... Hydrogen storage container 42 ... Pressure gauge (pressure maintaining means)
42a ... Valve (pressure maintaining means)
47. Gas control valve (pressure maintaining means)
DESCRIPTION OF SYMBOLS 50 ... Rolled aluminum 501 ... Sheet-like aluminum 502 ... Water-absorbing sheet 503 ... Granular calcium hydroxide

Claims (10)

  1. 　水と金属アルミニウムの反応を利用して水素ガスを製造する水素製造装置であって、
    　a) 筒状の外周壁部と、該外周壁部の内側に配置された、該外周壁部との間に環状空間を形成する筒状の内周壁部とを備えた水素発生容器と、
    　b) 前記環状空間に縦置き状態で収容された１又は複数枚のシート状アルミニウムと、
    　c) 前記水素発生容器内に収容された粒状の水酸化カルシウムと、
    　d) 前記水素発生容器に設けられた該水素発生容器内に水を供給するための水供給口と、
    　e) 前記環状空間の上部に位置するように前記水素発生容器に設けられた該水素発生容器内に発生した水素を取り出すための水素取出口と
    　を備えることを特徴とする水素製造装置。     A hydrogen production apparatus for producing hydrogen gas using a reaction between water and metal aluminum,
    a) a hydrogen generation container including a cylindrical outer peripheral wall portion and a cylindrical inner peripheral wall portion that is disposed inside the outer peripheral wall portion and forms an annular space between the outer peripheral wall portion;
    b) one or more sheet-like aluminum accommodated in the annular space in a vertically placed state;
    c) granular calcium hydroxide contained in the hydrogen generation vessel;
    d) a water supply port for supplying water into the hydrogen generation container provided in the hydrogen generation container;
    e) a hydrogen production apparatus comprising: a hydrogen outlet for taking out hydrogen generated in the hydrogen generation container provided in the hydrogen generation container so as to be positioned above the annular space.
  2. 　前記水素発生容器内の圧力を１MPa未満に維持するための圧力維持手段を備えることを特徴とする請求項１に記載の水素製造装置。 The hydrogen production apparatus according to claim 1, further comprising pressure maintaining means for maintaining the pressure in the hydrogen generation container at less than 1 MPa.
  3. 　前記内周壁部を取り囲むように１枚の前記シート状アルミニウムを複数回巻回したロール状アルミニウムが前記環状空間に収容されていることを特徴とする請求項１又は２に記載の水素製造装置。 3. The hydrogen production apparatus according to claim 1, wherein roll-shaped aluminum obtained by winding one sheet-shaped aluminum a plurality of times so as to surround the inner peripheral wall portion is accommodated in the annular space.
  4. 　前記ロール状アルミニウムの各層の間にスペーサが介装されていることを特徴とする請求項３に記載の水素製造装置。 4. A hydrogen production apparatus according to claim 3, wherein a spacer is interposed between each layer of the rolled aluminum.
  5. 　前記スペーサが吸水性材料から構成され、該スペーサに前記粒状の水酸化カルシウムが保持されていることを特徴とする請求項４に記載の水素製造装置。 The hydrogen production apparatus according to claim 4, wherein the spacer is made of a water-absorbing material, and the granular calcium hydroxide is held in the spacer.
  6. 　前記水素発生容器が、上部開口を有する有底円筒状の容器本体と、該容器本体の上部開口を塞ぐ蓋部であって、前記容器本体内に入り込む有底円筒状の凹部を有する蓋部とを備え、
    　前記容器本体の側壁部が前記外周壁部を構成し、前記蓋部の凹部の側壁部が前記内周壁部を構成することを特徴とする請求項１～５のいずれかに記載の水素製造装置。     The hydrogen generating container has a bottomed cylindrical container body having an upper opening, and a lid part that closes the upper opening of the container body, the lid part having a bottomed cylindrical recess that enters the container body; With
    6. The hydrogen production apparatus according to claim 1, wherein a side wall portion of the container body constitutes the outer peripheral wall portion, and a side wall portion of the concave portion of the lid portion constitutes the inner peripheral wall portion. .
  7. 　前記外周壁部及び前記内周壁部の少なくとも一方を冷却するための冷却装置をさらに備えることを特徴とする請求項１～６のいずれかに記載の水素製造装置。 The hydrogen production apparatus according to any one of claims 1 to 6, further comprising a cooling device for cooling at least one of the outer peripheral wall portion and the inner peripheral wall portion.
  8. 　前記冷却装置は、前記外周壁部の外面に沿って巻装された、冷却水が流通する第１水冷管と、前記内周壁部の外面に沿って巻装された、冷却水が流通する第２水冷管とから構成されていることを特徴とする請求項７に記載の水素製造装置。 The cooling device includes a first water-cooled pipe that is wound along the outer surface of the outer peripheral wall portion and through which the cooling water flows and a cooling water that is wound along the outer surface of the inner peripheral wall portion. The hydrogen production apparatus according to claim 7, comprising two water-cooled tubes.
  9. 　前記水素取出口に接続された、水素に含まれる水分を除去するための水分除去装置を備えることを特徴とする請求項１～８のいずれかに記載の水素製造装置。 The hydrogen production apparatus according to any one of claims 1 to 8, further comprising a moisture removing device connected to the hydrogen outlet for removing moisture contained in hydrogen.
  10. 　筒状の外周壁部と、該外周壁部の内側に配置された、該外周壁部との間に環状空間を形成する筒状の内周壁部とを備え、
    　前記環状空間に水及び水素発生剤を収容し、前記水と前記水素発生剤の反応により水素を発生させる水素発生容器。     A cylindrical outer peripheral wall portion, and a cylindrical inner peripheral wall portion that is disposed inside the outer peripheral wall portion and that forms an annular space between the outer peripheral wall portion,
    A hydrogen generation container that contains water and a hydrogen generating agent in the annular space and generates hydrogen by a reaction between the water and the hydrogen generating agent.
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