WO2012140726A1 - Agent produisant de l'hydrogène, procédé pour la production d'hydrogène utilisant ledit agent produisant de l'hydrogène et dispositif pour la production d'hydrogène - Google Patents

Agent produisant de l'hydrogène, procédé pour la production d'hydrogène utilisant ledit agent produisant de l'hydrogène et dispositif pour la production d'hydrogène Download PDF

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Publication number
WO2012140726A1
WO2012140726A1 PCT/JP2011/059047 JP2011059047W WO2012140726A1 WO 2012140726 A1 WO2012140726 A1 WO 2012140726A1 JP 2011059047 W JP2011059047 W JP 2011059047W WO 2012140726 A1 WO2012140726 A1 WO 2012140726A1
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WO
WIPO (PCT)
Prior art keywords
hydrogen
water
powder
activated carbon
generating
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Application number
PCT/JP2011/059047
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English (en)
Japanese (ja)
Inventor
高森清人
景山剛行
柴田剛克
小柳津初男
Original Assignee
日本水素発電株式会社
株式会社Ｅｐｏｗｅ
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Application filed by 日本水素発電株式会社, 株式会社Ｅｐｏｗｅ filed Critical 日本水素発電株式会社
Priority to PCT/JP2011/059047 priority Critical patent/WO2012140726A1/fr
Publication of WO2012140726A1 publication Critical patent/WO2012140726A1/fr

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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
    • 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

Definitions

  • the present invention relates to a hydrogen generator capable of generating hydrogen when immersed in water, and a hydrogen generation method and a hydrogen generator using the hydrogen generator.
  • hydrogen has characteristics such as being colorless and odorless, having a high combustion temperature of 3000 ° C., and generating no carbon dioxide or harmful gas even when burned. Consideration of using it as a new energy source is underway. However, hydrogen as an energy source has not been practically used because its production cost is high.
  • Patent Documents 1 to 3 As conventional methods for generating hydrogen from water without using fossil fuels, for example, those described in Patent Documents 1 to 3 are known.
  • Patent Document 1 discloses a method in which a new surface not covered with an oxide film is generated by cutting / grinding aluminum or an aluminum alloy in water at room temperature, and hydrogen is generated by reacting the new surface with water. It is disclosed.
  • Patent Document 2 discloses a method for generating hydrogen by reacting aluminum powder or a mixed powder composed of aluminum powder and metal powder (for example, zinc powder) having a smaller ionization tendency than aluminum and water. Yes.
  • Patent Document 3 discloses a hydrogen generator composed of aluminum powder and calcium oxide powder. When this hydrogen generating agent is immersed in water, calcium oxide and water react to produce calcium hydroxide, and this calcium hydroxide and aluminum powder react to generate hydrogen.
  • Patent Document 1 cannot generate a large amount of hydrogen because sufficient reaction rate cannot be obtained unless water is heated from the outside.
  • Patent Document 2 since the method described in Patent Document 2 requires a thermal spraying device for obtaining aluminum powder or zinc-aluminum powder, enlargement and complexity of the device are inevitable, and hydrogen can be generated at low cost. There wasn't.
  • the hydrogen generating agent described in Patent Document 3 could not generate hydrogen in an amount that can be used as an energy source. Specifically, the amount of hydrogen that can be generated by this hydrogen generating agent can only generate electric power necessary for driving a mobile phone.
  • the present invention has been made in view of such circumstances, and the object of the present invention is to provide a hydrogen generator capable of generating hydrogen in a large amount at a low cost, and a hydrogen generation method using the hydrogen generator. And providing a hydrogen generator.
  • a hydrogen generator generates hydrogen when immersed in water, and (1) a zeolite powder containing at least Al, Si and an alkali metal and a calcium compound powder (2) activated carbon powder having a large number of micropores and a specific surface area of 1000 m 2 / g or more, and (3) ⁇ -iron silicide, and 100 parts by weight of the mixed powder. Then, the activated carbon powder and the ⁇ iron silicide are each 0.1 parts by weight or more.
  • the specific surface area of activated carbon powder is so preferable that it is large, and 1200 m ⁇ 2 > / g or more is more preferable.
  • the hydrogen generating agent preferably further contains 0.1 parts by weight or more of a magnesium compound, and the activated carbon powder is selected from cedar thinned wood, coconut shell, diatomaceous earth, flower, sawdust, tofu cake, rice husk and rice bran It is preferable to carbonize at least one plant material prepared.
  • the hydrogen generation method according to the present invention is a method using the hydrogen generator, and the powdery ⁇ -iron silicide is combined with at least the mixed powder and the activated carbon powder. It is characterized by being immersed in water and immersed.
  • another hydrogen generation method is a method using the above-mentioned hydrogen generating agent, wherein the ⁇ iron silicide is disposed on the inner surface in advance.
  • the water is stored, and at least the mixed powder and the activated carbon powder are put into the stored water and immersed therein.
  • a hydrogen generator generates hydrogen using the hydrogen generation method, and includes a container for storing water, at least the mixed powder, and the An inlet for charging activated carbon powder into the container, water temperature measuring means for measuring the temperature of the water stored in the container, and water volume measurement for measuring the amount of water stored in the container And a water injection means for injecting the water based on the measurement result of the water temperature measurement means and / or the water amount measurement means, and a hydrogen outlet for taking out the generated hydrogen.
  • the present invention it is possible to provide a hydrogen generating agent capable of generating a large amount of hydrogen at a low cost, and a hydrogen generating method and a hydrogen generating apparatus using the hydrogen generating agent. Further, according to the present invention, since it is not necessary to burn fossil fuel, hydrogen can be generated without placing a burden on the global environment.
  • the measurement results of the total hydrogen generation amount (A) to (C) are graphs showing the transition of the total hydrogen generation amount for 120 minutes, 48 hours, and 5 days, respectively.
  • FIG. 5 is a graph showing the hydrogen generation amount measurement results for each predetermined time, wherein (A) to (C) are graphs showing the generation amount every 5 minutes, every 2 hours, and every day. It is a schematic diagram for demonstrating the structure of the hydrogen generator which concerns on this invention.
  • the hydrogen generator according to the present invention generates hydrogen when immersed in water.
  • the mixed powder composed of zeolite powder and calcium compound powder is mixed with activated carbon powder, ⁇ -iron silicide ( ⁇ -FeSi 2 ), Is added.
  • ⁇ -FeSi 2 ⁇ -iron silicide
  • the hydrogen generator has a powder form as a whole, it can be stored and handled easily by forming it into a pellet or tablet by pressing.
  • Zeolite powder is silicon, aluminum, iron, magnesium, calcium, sodium, potassium, phosphorus, manganese, titanium dioxide, etc., as well as various zeolites containing trace amounts of strontium, rubidium, barium, zinc, sulfur, molybdenum, etc. , which are naturally produced including at least aluminum, silicon and alkali metals (eg, Mg, Rb, etc.).
  • mordenite-type zeolite, A-type zeolite, dolomite powder, or artificial zeolite powder obtained by processing slaked lime can also be used as the zeolite powder.
  • the calcium powder is, for example, calcium hydroxide (Ca (OH) 2 ) or calcium carbonate (CaCO 3 ).
  • Calcium carbonate powder can be obtained very inexpensively by washing, crushing, and sun-drying various oyster, scallop or pearl shells.
  • the content of zeolite powder is preferably about 40 to 70 parts by weight, and the content of calcium powder is about 50 to 60 parts by weight. Is preferred.
  • the content of the zeolite powder is less than 30 parts by weight, the generation amount of hydrogen is lowered and productivity is lowered. This is thought to be because too little zeolite powder contributes to the hydrogen generation reaction described later.
  • the rate of the hydrogen generation reaction described later is lowered, and the productivity is lowered.
  • the content of the calcium powder exceeds 62 parts by weight, unreacted calcium is included in the generated hydrogen, and calcium adheres to the inside of a pipe or the like for transporting the generated hydrogen, which is not preferable.
  • the activated carbon powder is carbonized vegetable material. Specifically, activated carbon powder is carbonized from low-cost and readily available plant materials such as cedar thinned wood, coconut shells, diatomaceous earth, flowers, sawdust, tofu lees, rice husks, and rice bran in a 400-800 ° C furnace. As a result, the charcoal was produced, and this charcoal was produced by heat treatment for a predetermined time (temperature: 400-800 ° C., time: 60-360 minutes) in a vacuum state of about 10 ⁇ 1 Pa to 10 ⁇ 5 Pa Is.
  • a predetermined time temperature: 400-800 ° C., time: 60-360 minutes
  • the activated carbon powder has a high carbon quality with a carbonization rate of 90% or more and a pH of 9.0 to 11.0. In addition, a large number of fine pores having a diameter of about 3 nm are formed on the surface of the activated carbon powder, and the specific surface area is 1000 m 2 / g or more.
  • the activated carbon powder has various fullerene shapes such as a soccer ball type, a carbon nanotube type, a bucky onion type, and a horn type.
  • ⁇ -iron silicide is a kind of so-called environmental semiconductor composed of elements that have a high Clarke number and are not toxic to the human body, and is known to emit electromagnetic waves in the band of several milliHz to several teraHz at room temperature. Yes.
  • ⁇ -iron silicide can be powdered and added to the mixed powder together with the activated carbon powder.
  • the addition amount of ⁇ iron silicide and activated carbon powder may be 0.1 parts by weight or more. That is, it becomes a hydrogen generator capable of generating a large amount of hydrogen over a long period of time by adding a small amount of ⁇ -iron silicide and activated carbon powder to the mixed powder by a hydrogen generation reaction described later.
  • ⁇ -iron silicide can be dispersed in a phenolic resin and placed at the bottom of a container for storing water to be used for the hydrogen generation reaction, or can be slurried and applied to the inside of the container. Even in this case, ⁇ -iron silicide can contribute to the hydrogen generation reaction described later.
  • immersion in the specification and claims of this application not only applies a hydrogen generating agent to stored water but also pre-applies ⁇ iron silicide constituting the hydrogen generating agent. It shall also include storing water in a previously prepared container.
  • the present invention by adding activated carbon powder and ⁇ -iron silicide to a mixed powder composed of zeolite powder and calcium compound powder, the known hydrogen generation reaction is promoted, and a large amount of hydrogen is generated in a short time. Hydrogen can be generated over a long period of time.
  • the hydrogen generating agent according to the first embodiment the mixed powder consisting of a zeolite powder 48g calcium hydroxide powder 50 g, cedar thinnings carbide or the like to give specific surface area 1000 m 2 / g or more 1 g of activated carbon powder and 1 g of ⁇ iron silicide powder were added to make a total of 100 g.
  • the hydrogen generator according to Example 2 is obtained by further adding 1 g of magnesium silicide (MgSi 2 ) powder to the hydrogen generator according to Example 1 to obtain 47 g of zeolite powder.
  • the hydrogen generator according to the conventional example is obtained by adding 49 g of zeolite powder without adding ⁇ -iron silicide.
  • each hydrogen generating agent was immersed in 500 ml of water stored in the glass container, and the amount of hydrogen generation for every fixed time was measured with the flow meter.
  • the water amount is maintained in the range of 45 to 90 ° C. by appropriately replenishing water, and the water amount is 300 ml. It was made not to fall below.
  • Example 1 black square
  • Example 2 outlined regular triangle
  • the total amount of hydrogen generated after 30 minutes is 180 L in the conventional example (asterisk), but 1332 L in Example 1 and 1607 L in Example 2.
  • Example 2 Compared Example 1 and Example 2, Example 2 to which magnesium silicide was further added had a larger amount of hydrogen generation for about 90 minutes immediately after the start of the experiment. This is presumably because magnesium silicide further promoted the hydrogen generation reaction. It was confirmed that even when MgO was added instead of magnesium silicide, the amount of hydrogen generation increased compared to the conventional type.
  • the hydrogen generator 1 introduces a hydrogen generating agent into a container 2 composed of a glass container body 2 a and a lid 2 b that seals the container body 2 a. And a water inlet 7 for taking out the generated hydrogen out of the container 2 and a water injection means 6 for storing water in the container 2.
  • the hydrogen generator 1 includes a water temperature measuring unit 4 for measuring the temperature of the water 8 stored in the container 2 and a water amount measuring unit 5 for measuring the amount of the water 8. Signals output from the water temperature measuring means 4 and the water amount measuring means 5 are input to the water injection means 6.
  • the water temperature measuring means 4 measures the temperature of the water 8 and the water amount measuring means 5 measures the amount of the water 8. Then, the water temperature measuring means 4 and the water amount measuring means 5 each output a signal corresponding to the measurement result.
  • the water injection means 6 replenishes the container 2 with an appropriate amount of new water. Thereby, it is prevented that the water temperature becomes too high or the water becomes too low.
  • the hydrogen generator 1 since the adjustment of the water temperature and the amount of water after the generation of hydrogen is automated and takes less time, the production cost of hydrogen can be reduced.
  • water is replenished based on both the water temperature and the amount of water, but may be replenished based on only one of them.
  • various kinds of natural and artificial zeolite powders, calcium compound powders other than calcium hydroxide, and activated carbon powders made of plant materials other than cedar thinning materials the same hydrogen generation effect as described above can be obtained.
  • the water in which the hydrogen generating agent is immersed is not limited to pure water, and even when tap water or seawater is used, the same hydrogen generating effect as described above can be obtained.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Fuel Cell (AREA)

Abstract

L'invention a pour objet un agent produisant de l'hydrogène permettant de produire de l'hydrogène à faible coût et en grandes quantités, un procédé pour la production d'hydrogène utilisant ledit agent produisant de l'hydrogène et un dispositif pour la production d'hydrogène. Cet agent produisant de l'hydrogène produit de l'hydrogène quand il est immergé dans de l'eau et il est caractérisé en ce qu'il comprend (1) une poudre mélangée composée d'une poudre de zéolite contenant au moins de l'Al, du Si et un métal alcalin et d'une poudre de composé du calcium, (2) une poudre de charbon actif ayant une pluralité de micropores et une surface spécifique supérieure ou égale à 1 000 m2/g et (3) un siliciure de fer β, la quantité de poudre de charbon actif et de siliciure de fer β étant supérieure ou égale à 0,1 partie en poids pour 100 parties en poids de la poudre mélangée.
PCT/JP2011/059047 2011-04-12 2011-04-12 Agent produisant de l'hydrogène, procédé pour la production d'hydrogène utilisant ledit agent produisant de l'hydrogène et dispositif pour la production d'hydrogène WO2012140726A1 (fr)

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Application Number Priority Date Filing Date Title
PCT/JP2011/059047 WO2012140726A1 (fr) 2011-04-12 2011-04-12 Agent produisant de l'hydrogène, procédé pour la production d'hydrogène utilisant ledit agent produisant de l'hydrogène et dispositif pour la production d'hydrogène

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PCT/JP2011/059047 WO2012140726A1 (fr) 2011-04-12 2011-04-12 Agent produisant de l'hydrogène, procédé pour la production d'hydrogène utilisant ledit agent produisant de l'hydrogène et dispositif pour la production d'hydrogène

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019049611A1 (fr) * 2017-09-08 2019-03-14 杉山　修 Procédé de fabrication d'hydrogène gazeux

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005170780A (ja) * 2003-11-18 2005-06-30 Japan Science & Technology Agency 水の分解装置及び分解方法並びに水分解用メカノ触媒
JP2006306700A (ja) * 2005-01-07 2006-11-09 Hitachi Maxell Ltd 水素発生材料、水素製造装置および燃料電池
JP2006335603A (ja) * 2005-06-02 2006-12-14 Nitto Denko Corp 水素発生剤及び水素発生方法
JP2009505927A (ja) * 2005-08-24 2009-02-12 エイチ２ ソーラー ゲーエムベーハー 水から水素と酸素を生成する方法、及びケイ素化合物を用いた水素と酸素の貯蔵方法
JP2009240749A (ja) * 2008-03-31 2009-10-22 Takuma Yoshikawa 超音波による電磁波励起強化法およびその適用機器
JP2010269946A (ja) * 2009-05-19 2010-12-02 Hatsuo Koyaizu 水素発生剤、及び水素ガスの発生方法、並びに水素ガス供給装置
WO2011048685A1 (fr) * 2009-10-22 2011-04-28 株式会社テラウィング Agent de production d'hydrogène, procédé de production d'hydrogène utilisant ledit agent de production d'hydrogène, et appareil de production d'hydrogène

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005170780A (ja) * 2003-11-18 2005-06-30 Japan Science & Technology Agency 水の分解装置及び分解方法並びに水分解用メカノ触媒
JP2006306700A (ja) * 2005-01-07 2006-11-09 Hitachi Maxell Ltd 水素発生材料、水素製造装置および燃料電池
JP2006335603A (ja) * 2005-06-02 2006-12-14 Nitto Denko Corp 水素発生剤及び水素発生方法
JP2009505927A (ja) * 2005-08-24 2009-02-12 エイチ２ ソーラー ゲーエムベーハー 水から水素と酸素を生成する方法、及びケイ素化合物を用いた水素と酸素の貯蔵方法
JP2009240749A (ja) * 2008-03-31 2009-10-22 Takuma Yoshikawa 超音波による電磁波励起強化法およびその適用機器
JP2010269946A (ja) * 2009-05-19 2010-12-02 Hatsuo Koyaizu 水素発生剤、及び水素ガスの発生方法、並びに水素ガス供給装置
WO2011048685A1 (fr) * 2009-10-22 2011-04-28 株式会社テラウィング Agent de production d'hydrogène, procédé de production d'hydrogène utilisant ledit agent de production d'hydrogène, et appareil de production d'hydrogène

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019049611A1 (fr) * 2017-09-08 2019-03-14 杉山　修 Procédé de fabrication d'hydrogène gazeux
US11465902B2 (en) 2017-09-08 2022-10-11 Osamu Sugiyama Method for producing hydrogen gas

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