JP2791182B2 - Hydrogen gas generator - Google Patents
Hydrogen gas generatorInfo
- Publication number
- JP2791182B2 JP2791182B2 JP2131103A JP13110390A JP2791182B2 JP 2791182 B2 JP2791182 B2 JP 2791182B2 JP 2131103 A JP2131103 A JP 2131103A JP 13110390 A JP13110390 A JP 13110390A JP 2791182 B2 JP2791182 B2 JP 2791182B2
- Authority
- JP
- Japan
- Prior art keywords
- component
- generating agent
- gas generating
- hydrogen gas
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は水素ガス発生剤に関し、さらに詳しくは水溶
液中でのガス発生開始時間を任意に調節することができ
る水素ガス発生剤に関する。Description: TECHNICAL FIELD The present invention relates to a hydrogen gas generating agent, and more particularly, to a hydrogen gas generating agent capable of arbitrarily adjusting the gas generation start time in an aqueous solution.
従来、信号用気球の充填ガス、燃料電池等に用いられ
る水素ガス発生剤としては、水と反応して水素ガスを発
生する水素化硼素ナトリウム（NaBH4）などの第１成分
と、該第１成分の反応を促進させる、塩化コバルト（Co
Cl2）、塩化ニッケル（NiCl2）、塩化ラジウム（RhC
l2）、酸化白金系触媒等の第２成分との混合物が知られ
ており、これらのうち特にNaBH4とCoCl2との混合物が多
く使用されている。この混合物は、下記式（１）のよう
に水と容易に反応して水素ガスを発生する。Conventionally, as a filling gas for a signal balloon, a hydrogen gas generating agent used for a fuel cell or the like, a first component such as sodium borohydride (NaBH 4 ) that reacts with water to generate a hydrogen gas, Cobalt chloride (Co
Cl 2 ), nickel chloride (NiCl 2 ), radium chloride (RhC
l 2 ), a mixture with a second component such as a platinum oxide-based catalyst is known, and among these, a mixture of NaBH 4 and CoCl 2 is particularly frequently used. This mixture easily reacts with water to generate hydrogen gas as shown in the following formula (1).
NaBH4＋2H2O→NaBO2＋4H2↑（１） また上記第１成分と第２成分の混合物に、第３成分と
して、オルト硼酸（H3BO3）、メタ硼酸（HBO2）または
硬水軟化剤として炭酸ナトリウム（Na2CO3）、リン酸ナ
トリウム（Na3PO4）等を添加することにより、水中のみ
ならず海水などの塩を含む水溶液中での上記式（１）の
加水分解反応が可能となる。NaBH 4 + 2H 2 O → NaBO 2 + 4H 2 ↑ (1) Also, as a third component, orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) or hard water softening is added to the mixture of the first and second components. By adding sodium carbonate (Na 2 CO 3 ), sodium phosphate (Na 3 PO 4 ) or the like as an agent, the hydrolysis reaction of the above formula (1) not only in water but also in an aqueous solution containing salts such as seawater. Becomes possible.
第７図は、従来のガス発生剤ペレットの斜視図であ
る。このガス発生剤ペレット１は、上記第１成分、第２
成分および第３成分の混合薬剤を円筒状に圧縮成形して
得られるガス発生剤２と、該ガス発生剤２の側面に設け
られた断熱剤４とからなる。FIG. 7 is a perspective view of a conventional gas generating agent pellet. The gas generating agent pellet 1 is composed of the first component and the second component.
It comprises a gas generating agent 2 obtained by compression-molding a mixed drug of the component and the third component into a cylindrical shape, and a heat insulating agent 4 provided on a side surface of the gas generating agent 2.
このようなガス発生剤ペレット１は、水温が低い場合
でもガス発生剤２の反応熱によりガス発生速度の低下を
防止することができる。また混合薬剤が圧縮されたペレ
ットであるため、単位体積当たりのガス発生量が大き
く、取り扱いが容易である。さらに反応促進剤（第２成
分）の含有量およびそのペレットの高さを変化させたガ
ス発生剤ペレットを、要求されるガス発生特性に応じて
種々組み合わせて用いることにより、任意のガス発生時
間および最大ガス発生速度を得ることができる利点を有
する。Such a gas generating agent pellet 1 can prevent a decrease in the gas generation rate due to the reaction heat of the gas generating agent 2 even when the water temperature is low. In addition, since the mixed drug is a compressed pellet, the amount of gas generated per unit volume is large, and handling is easy. Further, by using various combinations of gas generating agent pellets in which the content of the reaction accelerator (second component) and the height of the pellets are changed according to the required gas generating characteristics, it is possible to obtain an arbitrary gas generating time and This has the advantage that the maximum gas generation rate can be obtained.
しかしながら、上記ガス発生剤ペレットでは、水溶液
中への投入と同時にガス発生剤が水溶液と接触するた
め、投入と同時に加水分解反応を開始してしまい、投入
してから一定時間後にガスの発生を開始させることがで
きなかった。However, in the above-mentioned gas generating agent pellets, the gas generating agent comes into contact with the aqueous solution at the same time as the charging into the aqueous solution, so that the hydrolysis reaction starts at the same time as the charging and the gas generation starts after a certain time after the charging. I couldn't let it.
本発明の目的は、上記従来技術の問題を解決し、ガス
発生剤を水溶液中に投入した後のガスの発生の開始時間
を任意に遅延させることができる水素ガス発生剤を提供
することにある。An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a hydrogen gas generating agent capable of arbitrarily delaying the start time of gas generation after the gas generating agent is put into an aqueous solution. .
本発明は、水と反応してガスを発生する周期律表Ia族
の少なくとも１種の元素と周期律表IIIb族の少なくとも
１種の元素との錯水素化物からなる第１成分と、標準電
極電位が亜鉛より貴である遷移金属元素から選ばれた少
なくとも１種の金属の化合物からなる第２成分と、硼
酸、酸化硼素、リン酸塩、炭酸塩、エチレンジアミン四
酢酸、ニトリロトリ酢酸、蓚酸、酒石酸およびこれらの
塩から選ばれた少なくとも１種の化合物からなる第３成
分とを含有する水素ガス発生剤において、前記水素ガス
発生剤の水溶液と接触する部分を前記第３成分で被覆し
たことを特徴とする水素ガス発生剤に関する。The present invention relates to a first component comprising a complex hydride of at least one element of Group Ia of the periodic table and at least one element of Group IIIb of the periodic table, which reacts with water to generate a gas; A second component comprising a compound of at least one metal selected from transition metal elements having a potential higher than zinc, and boric acid, boron oxide, phosphate, carbonate, ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxalic acid, tartaric acid And a third component comprising at least one compound selected from salts thereof, wherein a portion of the hydrogen gas generating agent that is in contact with the aqueous solution of the hydrogen gas generating agent is coated with the third component. And a hydrogen gas generating agent.
本発明における第３成分は、ガス発生剤に含まれる上
記３成分のうち、水溶液に対する溶解速度が最も小さ
く、溶けにくい性質を有する。したがって、ガス発生剤
と水溶液とが接触する反応面を第３成分で被覆すること
により、水溶液中に投入した後のガス発生剤の反応面と
水溶液とが接触してガスを発生するまでの時間を遅らせ
ることができる。さらに該第３成分の被覆量を変化させ
て水溶液中での溶解時間を調節することにより、ガスの
発生開始時間を任意に調整することが可能となる。The third component in the present invention has the lowest dissolution rate in an aqueous solution among the three components contained in the gas generating agent, and has a property of being hardly soluble. Therefore, by coating the reaction surface where the gas generating agent and the aqueous solution come into contact with each other with the third component, the time until the reaction surface of the gas generating agent comes into contact with the aqueous solution after the introduction into the aqueous solution to generate gas. Can be delayed. Further, by adjusting the dissolution time in the aqueous solution by changing the coating amount of the third component, the gas generation start time can be arbitrarily adjusted.
本発明の水素ガス発生剤は、例えば上記第１成分、第
２成分および第３成分を、要求されるガス発生特性に応
じてその量を調節して混合し、該混合薬剤を圧縮成型し
てガス発生剤ペレットとして用いられる。該水素ガス発
生剤は、水中のみならず海水などの塩を含む水溶液での
水素ガス発生が可能である。これは第３成分が塩を含む
水溶液中において第１成分の反応促進剤として使用し、
加水分解反応における水素ガス生成の抑制作用を低減さ
せるためである。The hydrogen gas generating agent of the present invention is obtained by, for example, mixing the first component, the second component, and the third component by adjusting the amounts thereof in accordance with required gas generating characteristics, and compression-molding the mixed agent. Used as gas generant pellets. The hydrogen gas generating agent can generate hydrogen gas not only in water but also in an aqueous solution containing a salt such as seawater. This is used as a reaction accelerator for the first component in an aqueous solution in which the third component contains a salt,
This is for reducing the effect of suppressing the production of hydrogen gas in the hydrolysis reaction.
以下、本発明を実施例により詳しく説明する。 Hereinafter, the present invention will be described in more detail with reference to Examples.
実施例１ 第１図は、本発明の一実施例を示す水素ガス発生剤ペ
レットの斜視図、第２図は、第１図の水素ガス発生剤ペ
レットの組立図である。Example 1 FIG. 1 is a perspective view of a hydrogen gas generating agent pellet showing one embodiment of the present invention, and FIG. 2 is an assembly diagram of the hydrogen gas generating agent pellet of FIG.
第１図および第２図において、ガス発生剤ペレット１
は、第１成分（NaBH4）、第２成分（CoCl2）および第３
成分（H3BO3）からなる圧縮成型された円筒状のガス発
生剤２と、該ガス発生剤２の上下面に形成された第３成
分層（H3BO3）３と、該ガス発生剤２および第３成分層
３の側面に設けられた断熱剤４とからなる。このガス発
生剤ペレット１は、水溶液中に投入されると、まず上下
に形成された第３成分層３と水溶液とが接触してH3BO3
が溶解を開始する。この溶解時間は第３成分層３の厚さ
を調整することにより任意に調整することができる。第
３成分が溶解されてガス発生剤２の表面が水溶液と接触
すると、上記した式（１）の加水分解反応が生じ、水素
ガスを発生する。該ガス発生剤ペレット１には断熱剤４
が設けられているため、水温が低い場合でも、加水分解
の反応熱を有効に利用でき、ガス発生速度が低下するこ
とがない。In FIG. 1 and FIG.
Are the first component (NaBH 4 ), the second component (CoCl 2 ) and the third component
And component (H 3 BO 3) compression molded consisting a cylindrical gas generating agent 2, the third component layer formed on the upper and lower surfaces of the gas generating agent 2 and (H 3 BO 3) 3, the gas generator And a heat insulating agent 4 provided on the side surface of the third component layer 3. When the gas generating agent pellets 1 are put into an aqueous solution, firstly, the third component layer 3 formed above and below is brought into contact with the aqueous solution and H 3 BO 3
Begins to dissolve. This dissolution time can be arbitrarily adjusted by adjusting the thickness of the third component layer 3. When the third component is dissolved and the surface of the gas generating agent 2 comes into contact with the aqueous solution, the hydrolysis reaction of the above formula (1) occurs, and hydrogen gas is generated. The gas generating agent pellet 1 has a heat insulating agent 4
Is provided, even when the water temperature is low, the heat of hydrolysis reaction can be effectively used, and the gas generation rate does not decrease.
第３図は、ガス発生剤およびH3BO3のそれぞれ1gを、5
00kg/cm2の荷重をかけて直径13mm、高さ7mmのペレット
状とし、このペレットを１の水に投入したときのペレ
ットの溶解速度を示す図である。ガス発生剤は水中に投
入後20〜30秒ですべて溶解するが、H3BO3は１分経過し
ても約0.4g程度しか溶解しない。したがって、H3BO3の
水に対する溶解速度が小さいという特性を利用してガス
発生剤からのガスの発生開始を遅延させることができ
る。H3BO3の溶解速度は、成型圧力によっても若干異な
るが、成型圧力500kg/cm2で圧縮成型したペレット状と
した場合には、H3BO3の消失（溶解）速度は3mm/minとな
るため、ガス発生剤の反応面にH3BO3を3mm被覆すれば、
約１分間ガス発生時間を遅延できることになる。第４図
には、H3BO3被覆の厚さとガス発生遅延時間との関係を
示した。FIG. 3 shows that 1 g of each of the gas generating agent and H 3 BO 3
FIG. 4 is a view showing the dissolution rate of a pellet when a pellet having a diameter of 13 mm and a height of 7 mm is formed by applying a load of 00 kg / cm 2 and the pellet is poured into one piece of water. The gas generating agent completely dissolves in water for 20 to 30 seconds after being put into water, but only about 0.4 g of H 3 BO 3 dissolves even after 1 minute. Therefore, the start of gas generation from the gas generating agent can be delayed by utilizing the characteristic that the dissolution rate of H 3 BO 3 in water is low. The dissolution rate of H 3 BO 3 is slightly different depending on the molding pressure. However, in the case of a pellet formed by compression molding at a molding pressure of 500 kg / cm 2 , the disappearance (dissolution) rate of H 3 BO 3 is 3 mm / min. Therefore, if 3 mm of H 3 BO 3 is coated on the reaction surface of the gas generating agent,
The gas generation time can be delayed for about one minute. FIG. 4 shows the relationship between the thickness of the H 3 BO 3 coating and the gas generation delay time.
ガス発生剤は水との反応性が高く大気中の水分とも容
易に反応するため、湿度の高い大気中に長時間放置する
ことはできないが、第３成分のH3BO3は単独では水とは
反応せず、また吸湿性も小さいため、この第３成分でガ
ス発生剤を被覆した本発明のガス発生剤ペレットは、ガ
ス発生剤と大気中の水分との接触を防ぐことができ、大
気中での安定性が向上し、取り扱いが容易となる。Since the gas generating agent to water with readily reaction of the reactive high atmospheric water, can not be left for a long time in a humid atmosphere, H 3 BO 3 of the third component alone and water Does not react and has low hygroscopicity. Therefore, the gas generant pellet of the present invention coated with the gas generant with the third component can prevent contact between the gas generant and moisture in the atmosphere, The stability in the inside is improved, and handling becomes easy.
実施例２ 第５図は、本発明の他の実施例を示すガス発生剤ペレ
ットの斜視図、第６図は、第５図のVI−VI線断面図であ
る。このガス発生剤ペレット１は、第１成分、第２成分
および第３成分からなる圧縮成型された円筒状のガス発
生剤２と、該ガス発生剤２の表面全体を被覆する第３成
分層（H3BO3層）３とからなる。該ペレット１を水中に
投入すると、まず表面のH3BO3が水に接触して溶解し、
該H3BO3が溶解して消失するまでの間、ペレットからの
ガス発生が遅延される。H3BO3の被覆層がなくなるとガ
ス発生剤ペレットのガス発生剤と水とが接触してペレッ
ト全面からガスが発生する。Example 2 FIG. 5 is a perspective view of a gas generating agent pellet showing another example of the present invention, and FIG. 6 is a sectional view taken along line VI-VI of FIG. The gas generating agent pellet 1 includes a compression-molded cylindrical gas generating agent 2 composed of a first component, a second component, and a third component, and a third component layer (which covers the entire surface of the gas generating agent 2). H 3 BO 3 layers) 3. When the pellet 1 is put into water, first, H 3 BO 3 on the surface is dissolved by contact with water,
Gas generation from the pellets is delayed until the H 3 BO 3 dissolves and disappears. When the H 3 BO 3 coating layer disappears, the gas generating agent of the gas generating agent pellet comes into contact with water, and gas is generated from the entire surface of the pellet.
本発明の水素ガス発生剤は、水に対する溶解度の小さ
い第３成分でその表面が被覆されているため、水溶液中
に投入後のガスの発生開始時間を遅延させることができ
る。また第３成分の被覆量を調整することにより、任意
にガス発生開始時間を調節することができる。さらに第
３成分でガス発生剤を被覆により、ガス発生剤と大気中
の水分との接触をなすことができるため、水素ガス発生
剤の大気中での安定性および取扱性が向上する。Since the surface of the hydrogen gas generating agent of the present invention is coated with the third component having low solubility in water, it is possible to delay the gas generation start time after being introduced into the aqueous solution. Further, by adjusting the coating amount of the third component, the gas generation start time can be arbitrarily adjusted. Further, by coating the gas generating agent with the third component, the gas generating agent can be brought into contact with the moisture in the atmosphere, so that the stability and handling property of the hydrogen gas generating agent in the atmosphere are improved.
第１図は、本発明の一実施例を示す水素ガス発生剤ペレ
ットの斜視図、第２図は、第１図のペレットの組立図、
第３図は、ガス発生剤とH3BO3の水に対する溶解速度を
示す図、第４図は、H3BO3被覆の厚さとガス発生遅延時
間との関係を示す図、第５図は、本発明の他の実施例を
示すガス発生剤ペレットの斜視図、第６図は、第５図の
VI−VI線断面図、第７図は、従来のガス発生剤ペレット
の斜視図である。 １…ガス発生剤ペレット、２…ガス発生剤、３…第３成
分層（H3BO3）、４…断熱剤。FIG. 1 is a perspective view of a hydrogen gas generating agent pellet showing one embodiment of the present invention, FIG. 2 is an assembly view of the pellet of FIG. 1,
FIG. 3 is a diagram showing the dissolution rate of the gas generating agent and H 3 BO 3 in water, FIG. 4 is a diagram showing the relationship between the thickness of the H 3 BO 3 coating and the gas generation delay time, and FIG. FIG. 6 is a perspective view of a gas generating agent pellet showing another embodiment of the present invention, and FIG.
FIG. 7 is a sectional view taken along the line VI-VI, and FIG. 7 is a perspective view of a conventional gas generating agent pellet. 1 ... gas generating agent pellet, 2 ... a gas generating agent, 3 ... third component layer (H 3 BO 3), 4 ... insulation agent.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 横林 照之 広島県呉市宝町６番９号 バブコック日 立株式会社呉工場内 (56)参考文献 特開 平１−257101（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C01B 3/08 C01B 6/15──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Teruyuki Yokobayashi 6-9 Takara-cho, Kure-shi, Hiroshima Pref. Surveyed field (Int.Cl. 6 , DB name) C01B 3/08 C01B 6/15
Claims (1)
の少なくとも１種の元素と周期律表IIIb族の少なくとも
１種の元素との錯水素化物からなる第１成分と、標準電
極電位が亜鉛より貴である遷移金属元素から選ばれた少
なくとも１種の金属の化合物からなる第２成分と、硼
酸、酸化硼素、リン酸塩、炭酸塩、エチレンジアミン四
酢酸、ニトリロトリ酢酸、蓚酸、酒石酸およびこれらの
塩から選ばれた少なくとも１種の化合物からなる第３成
分とを含有する水素ガス発生剤であって、前記水素ガス
発生剤の水と接触する部分を前記第３成分で被覆したこ
とを特徴とする水素ガス発生剤。1. A first component comprising a complex hydride of at least one element of Group Ia of the periodic table and at least one element of Group IIIb of the periodic table, which generates a gas by reacting with water, A second component comprising a compound of at least one metal selected from transition metal elements having an electrode potential nobleer than zinc, boric acid, boron oxide, phosphate, carbonate, ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxalic acid, A hydrogen gas generator containing a third component comprising at least one compound selected from tartaric acid and salts thereof, wherein a portion of the hydrogen gas generator that comes into contact with water is coated with the third component. A hydrogen gas generating agent, characterized in that:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2131103A JP2791182B2 (en) | 1990-05-21 | 1990-05-21 | Hydrogen gas generator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2131103A JP2791182B2 (en) | 1990-05-21 | 1990-05-21 | Hydrogen gas generator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0426501A JPH0426501A (en) | 1992-01-29 |
| JP2791182B2 true JP2791182B2 (en) | 1998-08-27 |
Family
ID=15050051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2131103A Expired - Fee Related JP2791182B2 (en) | 1990-05-21 | 1990-05-21 | Hydrogen gas generator |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2791182B2 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5804329A (en) * | 1995-12-28 | 1998-09-08 | National Patent Development Corporation | Electroconversion cell |
| GB9700168D0 (en) * | 1997-01-07 | 1997-02-26 | British Nuclear Fuels Plc | Hydrogen gas generation |
| JP4802360B2 (en) * | 2000-10-30 | 2011-10-26 | トヨタ自動車株式会社 | Hydrogen gas generator |
| JP4792632B2 (en) * | 2000-11-15 | 2011-10-12 | トヨタ自動車株式会社 | Hydrogen gas generator |
| JP2006298670A (en) * | 2005-04-18 | 2006-11-02 | Sony Corp | Method and apparatus for generating hydrogen and method and system for generating electrochemical energy |
| WO2007055146A1 (en) * | 2005-11-10 | 2007-05-18 | Hiromaito Co., Ltd. | Hydrogen-generating agent and use thereof |
| JP5014649B2 (en) * | 2006-03-09 | 2012-08-29 | 日東電工株式会社 | Hydrogen generator and hydrogen generation method |
| US8268028B2 (en) | 2007-03-26 | 2012-09-18 | Protonex Technology Corporation | Compositions, devices and methods for hydrogen generation |
| JP4489144B2 (en) * | 2007-04-12 | 2010-06-23 | 株式会社ヒロマイト | HYDROGEN GENERATOR, MANUFACTURING METHOD, AND HYDROGEN GENERATOR |
| TWI392644B (en) * | 2008-12-10 | 2013-04-11 | Univ Nat Central | The method of sodium borohydride reacting with water to produce hydrogen |
| CN102387986B (en) * | 2009-04-22 | 2015-09-09 | 罗姆股份有限公司 | Hydrogen production agent encapsulant, its manufacture method and hydrogen production process |
-
1990
- 1990-05-21 JP JP2131103A patent/JP2791182B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0426501A (en) | 1992-01-29 |
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