JP2007182336A - Method of generating hydrogen - Google Patents
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- JP2007182336A JP2007182336A JP2006000374A JP2006000374A JP2007182336A JP 2007182336 A JP2007182336 A JP 2007182336A JP 2006000374 A JP2006000374 A JP 2006000374A JP 2006000374 A JP2006000374 A JP 2006000374A JP 2007182336 A JP2007182336 A JP 2007182336A
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- 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
- C01B3/065—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 from a hydride
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- 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
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- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
Description
本発明は、水素発生方法に関する。 The present invention relates to a hydrogen generation method.
水素ガスの発生方法としては、水を電気分解する方法；金属と酸を反応させる方法；水素化金属に水を反応させる方法；メチルアルコールまたは天然ガスを水蒸気で改質する方法；水素吸蔵合金、活性炭、カーボンナノチューブ、リチウム−窒素系材料等の水素貯蔵材料から水素を放出させる方法等、各種の方法が知られている。しかしながら、これらの方法は、水素を発生させるために大量のエネルギーを必要とすることや、使用原料に対する水素発生量が少ないこと、大規模な設備を必要とすること等の欠点がある。このため、これらの方法は、工場規模での生産や実験室で用いる程度の量の水素発生には利用可能であるが、自動車搭載用燃料電池、携帯電話用、パーソナルコンピュータ用等のポータブル燃料電池等、所要量の水素燃料を継続的に供給でき、しかも小型化が要求される用途における水素供給方法としては不適切である。 Hydrogen gas can be generated by electrolyzing water; reacting metal with acid; reacting metal hydride with water; reforming methyl alcohol or natural gas with steam; hydrogen storage alloy; Various methods are known, such as a method of releasing hydrogen from hydrogen storage materials such as activated carbon, carbon nanotubes, and lithium-nitrogen materials. However, these methods have drawbacks such as requiring a large amount of energy to generate hydrogen, a small amount of hydrogen generation with respect to raw materials used, and a large-scale facility. For this reason, these methods can be used for production on a factory scale or generation of hydrogen in the amount used in laboratories, but portable fuel cells for automobile-mounted fuel cells, mobile phones, personal computers, etc. For example, it is unsuitable as a hydrogen supply method in applications where a required amount of hydrogen fuel can be continuously supplied and miniaturization is required.
一方、LiAlH4、NaBH4などの金属水素化合物は、水素化試薬として実験室等で用いられ
ているが、水と接触すると一時的に多量の水素を発生して爆発的現象をもたらすために、取り扱いを慎重にする必要があり、やはり上記した燃料電池の水素供給源として適するものではない。
On the other hand, metal hydrides such as LiAlH 4 and NaBH 4 are used in laboratories as hydrogenation reagents, but when they come into contact with water, a large amount of hydrogen is temporarily generated to cause an explosive phenomenon. It must be handled with care and is not suitable as a hydrogen supply source for the above-described fuel cell.
NaBH4等のテトラヒドロホウ酸塩のアルカリ性水溶液からの水素発生方法も報告されて
いるが、この方法では、アルカリ濃度（ｐＨ値）の制御が必要であり、しかも上記した通り、この化合物は取り扱いに注意が必要である（非特許文献１、２、特許文献１、２参照）。
A method for generating hydrogen from an alkaline aqueous solution of tetrahydroborate such as NaBH 4 has also been reported, but this method requires control of the alkali concentration (pH value). Attention is required (see Non-Patent Documents 1 and 2 and Patent Documents 1 and 2).
また、化学式：ＮＨ３ＢＨ３で表されるボラン・アンモニアの熱分解を利用して水素を放出させる方法も報告されているが、この方法は、高温に加熱して熱分解を生じさせるために、エネルギーを多量に必要とし、反応の制御も困難である（非特許文献３、非特許文献４）。 In addition, a method of releasing hydrogen by utilizing thermal decomposition of borane / ammonia represented by the chemical formula: NH 3 BH 3 has been reported, but this method is used to cause thermal decomposition by heating to high temperature. In addition, a large amount of energy is required, and control of the reaction is difficult (Non-patent Documents 3 and 4).
最近、水の存在下に、白金、パラジウム、ニッケル、コバルト、ロジウム、またはこれらの金属を含む化合物を触媒としたボラン・アンモニアの加水分解を利用した水素発生方法が報告されている（非特許文献５）。この反応では、高温に加熱することなく、制御可能な条件下において水素を発生させることが可能であるが、触媒としては主として貴金属が用いられているために、より低コスト化することが望まれており、また、水素の発生効率の点でも更なる改善が望まれている。
本発明は、上記した従来技術の現状に鑑みてなされたものであり、その主な目的は、燃料電池の燃料等として用いる水素ガスを、高温に加熱することなく、制御可能な条件下で発生させることができ、しかも低コストで効率よく水素ガスを発生できる方法を提供することである。 The present invention has been made in view of the above-described current state of the prior art, and its main purpose is to generate hydrogen gas used as fuel for fuel cells, etc. under controllable conditions without heating to high temperatures. And providing a method capable of generating hydrogen gas efficiently at low cost.
本発明者は、上記した目的を達成すべく鋭意研究を重ねてきた。その結果、ボラン・アンモニアNH3BH3を水素発生源とする水素発生方法において、特定の金属成分を無機酸化物に担持させた金属担持触媒を用いる場合には、比較的少ない触媒金属の使用量であっても、効率良く水素ガスを発生させることができ、しかも、水素発生量、発生速度等に制御も容易であることを見出し、ここに本発明を完成するに至った。 The present inventor has intensively studied to achieve the above-described object. As a result, in a hydrogen generation method using borane / ammonia NH 3 BH 3 as a hydrogen generation source, when using a metal-supported catalyst in which a specific metal component is supported on an inorganic oxide, a relatively small amount of catalyst metal is used. Even so, it has been found that hydrogen gas can be generated efficiently, and that the amount of hydrogen generated, the generation speed, etc. can be easily controlled, and the present invention has been completed here.
即ち、本発明は、下記の水素発生方法及び燃料電池への水素供給方法を提供するものである。
１． 水の存在下において、化学式：ＮＨ３ＢＨ３で表されるボラン・アンモニアを、周期表の８族に属する元素、周期表の９族に属する元素、周期表の１０族に属する元素、及び周期表の１１族に属する元素からなる群から選ばれた少なくとも一種の金属成分を無機酸化物担体に担持させた金属担持触媒に接触させることを特徴とする水素発生方法。
２． 金属担持触媒が、白金、パラジウム、ロジウム、ルテニウム、ニッケル、コバルト及び銅からなる群から選ばれた少なくとも一種の金属成分を無機酸化物担体に担持させたものである上記項１に記載の水素発生方法。
３． 無機酸化物担体が、アルミナ、シリカ、チタニア及びジルコニアからなる群から選ばれた少なくとも一種の金属酸化物である上記項１又は２に記載の水素発生方法。
４． 上記項１〜３のいずれかの方法によって発生させた水素を燃料電池の水素源とすることを特徴とする、燃料電池への水素供給方法。
That is, the present invention provides the following hydrogen generation method and hydrogen supply method to the fuel cell.
1. In the presence of water, borane / ammonia represented by the chemical formula: NH 3 BH 3 is converted into an element belonging to Group 8 of the periodic table, an element belonging to Group 9 of the periodic table, an element belonging to Group 10 of the periodic table, and the period. A method for generating hydrogen, comprising contacting a metal-supported catalyst in which at least one metal component selected from the group consisting of elements belonging to Group 11 in the table is supported on an inorganic oxide support.
2. Item 2. The hydrogen generation according to Item 1, wherein the metal-supported catalyst is obtained by supporting at least one metal component selected from the group consisting of platinum, palladium, rhodium, ruthenium, nickel, cobalt, and copper on an inorganic oxide support. Method.
3. Item 3. The method for generating hydrogen according to Item 1 or 2, wherein the inorganic oxide carrier is at least one metal oxide selected from the group consisting of alumina, silica, titania and zirconia.
4). A method for supplying hydrogen to a fuel cell, wherein the hydrogen generated by the method according to any one of Items 1 to 3 is used as a hydrogen source for the fuel cell.
本発明の水素発生方法では、水素発生成分として、化学式：ＮＨ３ＢＨ３で表されるボラン・アンモニアを用いる。ボラン・アンモニアは公知化合物であり、密度が0.74 g/cm3の無色の化合物である。ボラン・アンモニアは、水に可溶であるが、室温付近の温度では水との反応は生じ難く、比較的安定な水溶液として存在し、その取り扱いは容易且つ安全である。例えば、ボラン・アンモニアの1.0重量％水溶液を室温でアルゴン雰囲気下に放
置した際の放置直後、６日経過後、及び３０日経過後のそれぞれの１１B NMRスペクトル
を測定した結果、ＮＨ３ＢＨ３に帰属されるピーク(δ=-24 ppm)はほとんど変化せず、１ヶ月経過後にも新たなピークは観測されなかった。この結果は、NH3BH3は室温で１ヶ月経過しても水とほとんど反応しないことを示すものである。
In the hydrogen generation method of the present invention, borane / ammonia represented by the chemical formula: NH 3 BH 3 is used as a hydrogen generation component. Borane / ammonia is a known compound and is a colorless compound having a density of 0.74 g / cm 3 . Although borane / ammonia is soluble in water, it hardly reacts with water at a temperature around room temperature, exists as a relatively stable aqueous solution, and its handling is easy and safe. For example, as a result of measuring 11 B NMR spectra of a 1.0% by weight aqueous solution of borane / ammonia immediately after being left in an argon atmosphere at room temperature, after 6 days, and after 30 days, it is attributed to NH 3 BH 3 . The observed peak (δ = -24 ppm) hardly changed, and no new peak was observed even after one month. This result shows that NH 3 BH 3 hardly reacts with water even after one month at room temperature.
一方、本発明者の研究によれば、ボラン・アンモニアは、水の存在下に、特定の金属成分を無機酸化物担体に担持させた金属担持触媒と接触させることによって、下記化学反応式（１）に従って、水と速やかに反応して、水素を発生することが明らかとなった。 On the other hand, according to the study of the present inventor, borane / ammonia is brought into contact with a metal-supported catalyst in which a specific metal component is supported on an inorganic oxide support in the presence of water, whereby the following chemical reaction formula (1 ) To react quickly with water to generate hydrogen.
この反応では、水素発生量は、ＮＨ３ＢＨ３自体が分解して発生する水素と、水からの水素の和になるので、反応に関与するＮＨ３ＢＨ３とＨ２Ｏの合計量に対して８．９重量％の水素が発生し、水素の発生効率は非常に高くなる。 In this reaction, the amount of hydrogen generated is the sum of hydrogen generated by decomposition of NH 3 BH 3 itself and hydrogen from water, so the total amount of NH 3 BH 3 and H 2 O involved in the reaction is As a result, 8.9 wt% of hydrogen is generated, and the hydrogen generation efficiency becomes very high.
本発明の水素発生方法は、上記反応を利用する方法であり、ボラン・アンモニアを水素発生成分として用い、これを、水の存在下において、特定の金属成分を無機酸化物担体に担持させた金属担持触媒に接触させる方法である。 The hydrogen generation method of the present invention is a method utilizing the above reaction, using borane / ammonia as a hydrogen generation component, which is a metal in which a specific metal component is supported on an inorganic oxide support in the presence of water. This is a method of contacting with a supported catalyst.
以下、本発明方法について具体的に説明する。 Hereinafter, the method of the present invention will be specifically described.
金属担持触媒
本発明では、触媒として、周期表の８族に属する元素、周期表の９族に属する元素、周期表の１０族に属する元素、及び周期表の１１族に属する元素からなる群から選ばれた少なくとも一種の金属成分を無機酸化物担体に担持させた金属担持触媒を用いる。
Metal-supported catalyst In the present invention, the catalyst is selected from the group consisting of an element belonging to Group 8 of the periodic table, an element belonging to Group 9 of the periodic table, an element belonging to Group 10 of the periodic table, and an element belonging to Group 11 of the periodic table. A metal-supported catalyst in which at least one selected metal component is supported on an inorganic oxide carrier is used.
この様な特定の金属成分を担体に担持させた触媒は、貴金属のみからなる触媒と比較して、低コストであるばかりでなく、貴金属のみからなる触媒よりもボラン・アンモニアの加水分解反応に対して非常に高い活性を有するものである。従って、上記した金属担持触媒を用いることによって、低コストで効率良く水素ガスを発生させることが可能となる。 A catalyst in which such a specific metal component is supported on a carrier is not only lower in cost than a catalyst made of only a noble metal, but also has a higher reaction to hydrolysis of borane / ammonia than a catalyst made of only a noble metal. And has a very high activity. Therefore, by using the above metal-supported catalyst, it is possible to efficiently generate hydrogen gas at a low cost.
本発明で用いる金属担持触媒では、周期表の８族に属する元素としては、鉄、ルテニウム等を例示でき、周期表の９族に属する元素としては、コバルト、ロジウムなどを例示でき、周期表の１０族に属する元素としては、ニッケル、パラジウム、白金等を例示でき、周期表の１１族に属する元素としては、銅、銀、金等を例示できる。これらの金属成分は、一種単独または二種以上混合して用いることができる。 In the metal-supported catalyst used in the present invention, examples of the element belonging to Group 8 of the periodic table include iron and ruthenium. Examples of the element belonging to Group 9 of the periodic table include cobalt and rhodium. Examples of the element belonging to Group 10 include nickel, palladium, platinum and the like, and examples of the element belonging to Group 11 of the periodic table include copper, silver and gold. These metal components can be used individually by 1 type or in mixture of 2 or more types.
これらの金属成分の内で、特に、白金、パラジウム、ロジウム、ルテニウム、ニッケル、コバルト、銅等が好ましい。 Of these metal components, platinum, palladium, rhodium, ruthenium, nickel, cobalt, copper and the like are particularly preferable.
担体として用いる無機酸化物としては、例えば、金属酸化物、複合金属酸化物、ゼオライト、メソポーラスシリカ等の各種酸化物を用いることができる。好ましい担体の具体例としては、アルミナ、シリカ、チタニア、ジルコニアなどの金属酸化物を挙げることができる。 As the inorganic oxide used as the carrier, for example, various oxides such as metal oxide, composite metal oxide, zeolite, and mesoporous silica can be used. Specific examples of preferred carriers include metal oxides such as alumina, silica, titania and zirconia.
担体の形状、大きさ等については、特に限定的ではなく、上記した金属成分を担持可能な形状及び大きさであればよく、例えば、粉体、造粒物、成形物等の各種形状の無機酸化物を用いることができる。特に、担体が多孔質であれば、重量当たりの金属成分の担持量を多くすることができる点で有利である。 The shape, size, etc. of the carrier are not particularly limited as long as it is a shape and size capable of supporting the above-described metal component. For example, various shapes of inorganic materials such as powders, granulated products, molded products, etc. An oxide can be used. In particular, if the support is porous, it is advantageous in that the amount of metal component supported per weight can be increased.
上記金属担持触媒における金属成分の担持量については、具体的な反応温度、反応形態、担体の形状等によって最適な範囲を適宜決めればよいが、通常、金属成分と無機酸化物担体の合計量を１００重量％として、金属成分量を 0.1〜50重量％程度とすればよく、
0.5〜20重量％程度とすることが好ましい。
The supported amount of the metal component in the metal-supported catalyst may be appropriately determined according to the specific reaction temperature, reaction form, support shape, etc., but the total amount of the metal component and the inorganic oxide support is usually determined. 100% by weight, the amount of metal component should be about 0.1-50% by weight,
It is preferably about 0.5 to 20% by weight.
本発明の水素ガス発生方法において、特に高い触媒活性を示す金属担持触媒の具体例としては、ルテニウム担持シリカ触媒、白金担持アルミナ触媒、パラジウム担持チタニア触媒、ロジウム担持ジルコニア触媒、ニッケル担持アルミナ触媒、コバルト担持シリカ触媒、銅担持アルミナ触媒等を挙げることができる。 In the hydrogen gas generation method of the present invention, specific examples of the metal-supported catalyst exhibiting particularly high catalytic activity include ruthenium-supported silica catalyst, platinum-supported alumina catalyst, palladium-supported titania catalyst, rhodium-supported zirconia catalyst, nickel-supported alumina catalyst, cobalt Examples thereof include a supported silica catalyst and a copper supported alumina catalyst.
本発明では、金属担持触媒は、一種単独又は二種以上混合して用いることができる。 In the present invention, the metal-supported catalysts can be used singly or in combination of two or more.
金属成分を担体に担持させる方法については特に限定はなく、含浸法、析出沈殿法等の公知の調製法を適宜適用できる。例えば、含浸法によって金属担持触媒を調製する場合に
は、金属塩、無機酸化物担体及び水をフラスコ等の容器中で攪拌した後、水を蒸発させ、焼成した後、必要に応じて水素等の還元剤で処理することによって、目的とする金属担持触媒を得ることができる。水を蒸発させる方法については特に限定はなく、例えばポンプによる減圧、加熱等の手段を適宜採用できる。焼成温度についても特に限定はなく、一般的には、金属塩の分解温度付近または分解温度以上の温度とすることが望ましい。また、この様な焼成処理のみで金属成分が十分に還元されない場合には、必要に応じて、還元処理を行えばよい。還元処理としては、例えば、水素雰囲気中で適度な温度範囲に加熱する方法等を採用できる。また、本発明方法で用いる水素発生物質であるボラン・アンモニアも還元剤として作用するので、触媒金属として還元されやすい金属を用いる場合には、ボラン・アンモニアとの接触によって水素を発生させる際に、触媒金属を含む化合物も還元されて金属となるので、他の還元剤による還元処理を省略することができる。
The method for supporting the metal component on the carrier is not particularly limited, and known preparation methods such as an impregnation method and a precipitation method can be appropriately applied. For example, when preparing a metal-supported catalyst by an impregnation method, after stirring a metal salt, an inorganic oxide carrier and water in a container such as a flask, the water is evaporated and calcined, and hydrogen as necessary The target metal-supported catalyst can be obtained by treating with a reducing agent. The method for evaporating water is not particularly limited, and for example, means such as pressure reduction by a pump and heating can be appropriately employed. There are no particular limitations on the firing temperature, and it is generally desirable that the firing temperature be near or near the decomposition temperature of the metal salt. Further, when the metal component is not sufficiently reduced only by such a baking treatment, a reduction treatment may be performed as necessary. As the reduction treatment, for example, a method of heating to an appropriate temperature range in a hydrogen atmosphere can be employed. Further, since borane / ammonia, which is a hydrogen generating material used in the method of the present invention, also acts as a reducing agent, when using a metal that is easily reduced as a catalyst metal, when generating hydrogen by contact with borane / ammonia, Since the compound containing the catalytic metal is also reduced to a metal, the reduction treatment with another reducing agent can be omitted.
水素発生方法
本発明の水素発生方法は、化学式：ＮＨ３ＢＨ３で表されるボラン・アンモニアを水素発生成分として用い、水の存在下において、上記した金属担持触媒を水素発生成分であるボラン・アンモニアに接触させる方法である。
Hydrogen Generation Method The hydrogen generation method of the present invention uses borane / ammonia represented by the chemical formula: NH 3 BH 3 as a hydrogen generation component, and in the presence of water, the above metal-supported catalyst is a boron generation component that is a hydrogen generation component. This is a method of contacting with ammonia.
ボラン・アンモニアの種類について特に限定はなく、一般に市販されているものをそのまま使用できる。また、水素発生に悪影響の無い限りその他の成分が同時に含まれていても良い。 There is no limitation in particular about the kind of borane / ammonia, and what is generally marketed can be used as it is. Further, other components may be included at the same time as long as there is no adverse effect on the hydrogen generation.
水の存在下において、ボラン・アンモニアを金属担持触媒に接触させる方法については、特に限定はなく、例えば、ボラン・アンモニアと触媒の混合物に水を添加する方法；ボラン・アンモニアと触媒のいずれか一方又は両方をあらかじめ水溶液若しくは水分散液としておき、両者を混合する方法などを採用できる。これらの方法では、例えば、前者の場合には、水の添加速度、添加量などを調整することによって、水素の発生速度、発生量などを容易に制御できる。また、後者の場合には、ボラン・アンモニアと触媒の混合速度、混合割合、水溶液の濃度等を調整することによって、水素の発生速度、発生量などを容易に制御できる。 There is no particular limitation on the method of bringing borane / ammonia into contact with the metal-supported catalyst in the presence of water, for example, a method of adding water to a mixture of borane / ammonia and the catalyst; either one of borane / ammonia and the catalyst Alternatively, it is possible to employ a method in which both are previously prepared as an aqueous solution or an aqueous dispersion, and both are mixed. In these methods, for example, in the former case, the hydrogen generation rate, generation amount, and the like can be easily controlled by adjusting the water addition rate, addition amount, and the like. In the latter case, by adjusting the mixing rate, mixing ratio, concentration of the aqueous solution, and the like of borane / ammonia and the catalyst, the hydrogen generation rate, generation amount, etc. can be easily controlled.
上記反応式に示すように、ボラン・アンモニア１モルに対して水２モルが反応して水素が発生するので、原料として用いたボラン・アンモニアを十分に反応させるためには、水の使用量は、ボラン・アンモニア１モルに対して２モル程度以上とすることが好ましい。 As shown in the above reaction formula, 2 mol of water reacts with 1 mol of borane / ammonia to generate hydrogen, so in order to sufficiently react the borane / ammonia used as a raw material, the amount of water used is It is preferable that the amount be about 2 mol or more per 1 mol of borane / ammonia.
尚、ボラン・アンモニアの水への溶解度は、２３℃において約２６重量％であり、あらかじめ水溶液とする場合には、飽和濃度までの水溶液を用いることができるが、更に、飽和濃度を超えたボラン・アンモニアを不溶分として含む水溶液を用いても良い。 The solubility of borane / ammonia in water is about 26% by weight at 23 ° C., and when an aqueous solution is prepared in advance, an aqueous solution up to a saturated concentration can be used. An aqueous solution containing ammonia as an insoluble component may be used.
ボラン・アンモニア水溶液におけるボラン・アンモニア濃度の下限についても特に限定はなく、例えば、ボラン・アンモニア濃度が０．１重量％またはそれを下回る非常に低濃度の水溶液を用いることもできる。 The lower limit of the borane / ammonia concentration in the borane / ammonia aqueous solution is also not particularly limited. For example, an aqueous solution having a very low concentration of borane / ammonia concentration of 0.1% by weight or less can be used.
金属担持触媒の使用量については、使用量が多くなると水素発生反応を促進させることができるので、要求される水素発生速度やコストなどを考慮して適宜決めればよい。例えば、該金属担持触媒に担持されている触媒金属の量として、ボラン・アンモニア１モルに対して、０．００００１〜５モル程度という広い範囲から選択することが可能である。特に、反応速度、触媒コスト等のバランスを考慮すると、例えば、ボラン・アンモニア１モルに対して該金属担持触媒中に金属成分量を０．０００１〜０．１モル程度とすればよい。 The amount of the metal-supported catalyst used can be appropriately determined in consideration of the required hydrogen generation rate, cost, and the like because the hydrogen generation reaction can be promoted as the amount used increases. For example, the amount of catalyst metal supported on the metal-supported catalyst can be selected from a wide range of about 0.00001 to 5 moles per mole of borane / ammonia. In particular, considering the balance between reaction rate and catalyst cost, for example, the amount of metal component in the metal-supported catalyst may be about 0.0001 to 0.1 mol per mol of borane / ammonia.
水素発生反応の反応温度については、特に限定はないが、水の凝固点である０℃以上であって、８０℃程度以下であることが好ましく、１０〜５０℃程度であることがより好ましい。 The reaction temperature of the hydrogen generation reaction is not particularly limited, but is 0 ° C. or more, which is the freezing point of water, preferably about 80 ° C. or less, and more preferably about 10 to 50 ° C.
反応時の反応系内の圧力や雰囲気については特に限定はなく、適宜選択できる。 There is no limitation in particular about the pressure and atmosphere in the reaction system at the time of reaction, and it can select suitably.
水素発生方法の利用方法
本発明方法によって発生させた水素は、例えば、燃料電池用の燃料として燃料電池に直接供給することができる。特に、室温付近の温度で水素を発生させることができ、しかも水素発生速度、発生量等を制御可能であることから、自動車搭載用燃料電池；携帯電話用、パーソナルコンピュータ用等のポータブル燃料電池等の水素供給方法として有用性が高い方法である。
Utilization Method of Hydrogen Generation Method Hydrogen generated by the method of the present invention can be directly supplied to the fuel cell as fuel for the fuel cell, for example. In particular, since hydrogen can be generated at temperatures near room temperature, and the hydrogen generation rate, generation amount, etc. can be controlled, fuel cells for automobiles; portable fuel cells for mobile phones, personal computers, etc. This method is highly useful as a hydrogen supply method.
発生した水素については、例えば、水素吸蔵合金を充填した容器内に捕集して貯蔵することが可能である。また、水素吸蔵合金を用い、温度を平衡圧力―温度関係に従って調整することによって、発生した水素の系内圧力を制御することも可能である。 The generated hydrogen can be collected and stored in a container filled with a hydrogen storage alloy, for example. It is also possible to control the internal pressure of the generated hydrogen by using a hydrogen storage alloy and adjusting the temperature according to the equilibrium pressure-temperature relationship.
本発明の水素発生方法によれば、高温に加熱することなく、制御可能な条件下で効率よく水素ガスを発生させることができる。特に、本発明方法で用いる金属担持触媒は、金属成分量が少ない場合であっても、水素発生反応に対して高い活性を示し、短い反応時間で効率よく多量の水素を発生させることができる。このため、本発明の水素発生方法は、低コストで効率の良い水素発生方法として非常に有用性が高い方法である。 According to the hydrogen generation method of the present invention, hydrogen gas can be efficiently generated under controllable conditions without heating to a high temperature. In particular, the metal-supported catalyst used in the method of the present invention exhibits high activity for the hydrogen generation reaction even when the amount of the metal component is small, and can efficiently generate a large amount of hydrogen in a short reaction time. For this reason, the hydrogen generation method of the present invention is very useful as a low-cost and efficient hydrogen generation method.
本発明方法によって発生した水素ガスは、例えば、自動車搭載用燃料電池、ポータブル燃料電池等の燃料として有用性が高いものである。 The hydrogen gas generated by the method of the present invention is highly useful as a fuel for, for example, a fuel cell for automobiles and a portable fuel cell.
以下、実施例を挙げて本発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
実施例１
144 mgの塩化ルテニウム(RuCl3)、6 gのシリカ(SiO2)、及び10 mlの水(H2O)をフラスコにいれ、室温で１０分間攪拌し、70℃に加熱して、ポンプで減圧して水を蒸発させた。空気中で250℃、1時間焼成した後、試料に水素ガスをフロー(30 ml/min)しながら、400℃、1.5時間処理した。この処理によって、ルテニウム金属がシリカ上に担持された触媒（ル
テニウム及びシリカの合計量中、ルテニウム含有率1.1重量％）を得た。
Example 1
144 mg ruthenium chloride (RuCl 3 ), 6 g silica (SiO 2 ), and 10 ml water (H 2 O) are placed in a flask, stirred at room temperature for 10 minutes, heated to 70 ° C. and pumped The water was evaporated under reduced pressure. After baking in air at 250 ° C. for 1 hour, the sample was treated at 400 ° C. for 1.5 hours while flowing hydrogen gas (30 ml / min). By this treatment, a catalyst in which ruthenium metal was supported on silica (ruthenium content 1.1% by weight in the total amount of ruthenium and silica) was obtained.
上記方法で得られた触媒149 mgを容量30 mlの二つ口フラスコに入れ、その一つの口に
ガスビューレットを接続し、もう一つの口に50 ml の等圧型分液ロートを接続した。等圧型分液ロートには、100 mgのボラン・アンモニア(NH3BH3, 純度90%)を溶解した10 mlの水溶液を入れた。
149 mg of the catalyst obtained by the above method was placed in a 30-ml two-necked flask, a gas burette was connected to one of the necks, and a 50-ml isobaric separatory funnel was connected to the other. In an isobaric separatory funnel, 10 ml of an aqueous solution in which 100 mg of borane / ammonia (NH 3 BH 3 , purity 90%) was dissolved was added.
真空ポンプを用いて系内を排気し、アルゴンガス置換を行い、等圧型分液ロートから二つ口フラスコにボラン・アンモニア水溶液を流し込み、室温において攪拌を続けた。攪拌開始1分後に52 ml、２分後に110 ml、５分後に214 ml、7分後に214 mlのガス放出が観測
された。
The system was evacuated using a vacuum pump, purged with argon gas, a borane / ammonia aqueous solution was poured into the two-necked flask from the isobaric separatory funnel, and stirring was continued at room temperature. Gas release of 52 ml was observed 1 minute after the start of stirring, 110 ml after 2 minutes, 214 ml after 5 minutes, and 214 ml after 7 minutes.
ガスクロマトグラフィ（GC）及び質量分析(MS)を行った結果、放出ガスは水素であることが確認できた。水素放出量は、原料として用いたボラン・アンモニア(NH3BH3)に対して3.0倍モルであった。 As a result of performing gas chromatography (GC) and mass spectrometry (MS), it was confirmed that the released gas was hydrogen. The amount of hydrogen released was 3.0 times the mol of borane / ammonia (NH 3 BH 3 ) used as a raw material.
また、上記した方法で発生した水素ガスをそのまま固体高分子型燃料電池に導入して、燃料電池が作動することを確認した。 Further, it was confirmed that the hydrogen gas generated by the above-described method was directly introduced into the polymer electrolyte fuel cell and the fuel cell was operated.
実施例２
124 mgの塩化ルテニウム(RuCl3)、3 gのγ-アルミナ(γ-Al2O3)、及び10 mlの水(H2O)
をフラスコにいれ、室温で１０分間攪拌し、70℃に加熱して、ポンプで減圧して水を蒸発させた。空気中で300℃、５時間焼成した後、試料に水素ガスをフロー(50 ml/min)しながら、250℃、３時間処理した。この処理によって、ルテニウム金属がγ-アルミナ上に担持された触媒（ルテニウム及びアルミナの合計量中、ルテニウム含有率２重量％）を得た。
Example 2
124 mg ruthenium chloride (RuCl 3 ), 3 g γ-alumina (γ-Al 2 O 3 ), and 10 ml water (H 2 O)
Was stirred at room temperature for 10 minutes, heated to 70 ° C., and the pressure was reduced by a pump to evaporate water. After baking in air at 300 ° C. for 5 hours, the sample was treated at 250 ° C. for 3 hours while flowing hydrogen gas (50 ml / min). By this treatment, a catalyst in which ruthenium metal was supported on γ-alumina (ruthenium content 2% by weight in the total amount of ruthenium and alumina) was obtained.
上記方法で得られた触媒260 mgを容量30 mlの二つ口フラスコに入れ、その一つの口に
ガスビューレットを接続し、もう一つの口に50 ml の等圧型分液ロートを接続した。等圧型分液ロートには、100 mgのボラン・アンモニア(NH3BH3, 純度90%)を溶解した10 mlの水溶液を入れた。
260 mg of the catalyst obtained by the above method was placed in a two-necked flask having a volume of 30 ml, a gas burette was connected to one of the necks, and a 50 ml isobaric separatory funnel was connected to the other. In an isobaric separatory funnel, 10 ml of an aqueous solution in which 100 mg of borane / ammonia (NH 3 BH 3 , purity 90%) was dissolved was added.
真空ポンプを用いて系内を排気し、アルゴンガス置換を行い、等圧型分液ロートから二つ口フラスコにボラン・アンモニア水溶液を流し込み、室温において攪拌を続けた。攪拌開始30秒後に57 ml、1分後に113 ml、1分30秒後に177 ml、2分後に207 ml、３分後に213 mlのガス放出が観測された。 The system was evacuated using a vacuum pump, purged with argon gas, a borane / ammonia aqueous solution was poured into the two-necked flask from the isobaric separatory funnel, and stirring was continued at room temperature. Gas release of 57 ml was observed 30 seconds after the start of stirring, 113 ml after 1 minute, 177 ml after 1 minute 30 seconds, 207 ml after 2 minutes, and 213 ml after 3 minutes.
ガスクロマトグラフィ（GC）及び質量分析(MS)を行った結果、放出ガスは水素であることが確認できた。水素放出量は、原料として用いたボラン・アンモニア(NH3BH3)に対して3.0倍モルであった。 As a result of performing gas chromatography (GC) and mass spectrometry (MS), it was confirmed that the released gas was hydrogen. The amount of hydrogen released was 3.0 times the mol of borane / ammonia (NH 3 BH 3 ) used as a raw material.
また、上記した方法で発生した水素ガスをそのまま固体高分子型燃料電池に導入して、燃料電池が作動することを確認した。 Further, it was confirmed that the hydrogen gas generated by the above-described method was directly introduced into the polymer electrolyte fuel cell and the fuel cell was operated.
実施例３
104 mgの塩化白金(PtCl4)、3 gのγ-アルミナ(γ-Al2O3)、及び10 mlの水(H2O)をフラ
スコにいれ、室温で１０分間攪拌し、70℃に加熱して、ポンプで減圧して水を蒸発させた。空気中で300℃、５時間焼成した後、試料に水素ガスをフロー(50 ml/min)しながら、250℃、３時間処理した。この処理によって、白金がγ-アルミナ上に担持された触媒（白金及びアルミナの合計量中、白金含有率２重量％）を得た。
Example 3
104 mg of platinum chloride (PtCl 4 ), 3 g of γ-alumina (γ-Al 2 O 3 ), and 10 ml of water (H 2 O) were placed in a flask, stirred at room temperature for 10 minutes, and brought to 70 ° C. Heated and reduced pressure with a pump to evaporate the water. After baking in air at 300 ° C. for 5 hours, the sample was treated at 250 ° C. for 3 hours while flowing hydrogen gas (50 ml / min). By this treatment, a catalyst in which platinum was supported on γ-alumina (platinum content 2% by weight in the total amount of platinum and alumina) was obtained.
上記方法で得られた触媒509 mgを容量30 mlの二つ口フラスコに入れ、その一つの口に
ガスビューレットを接続し、もう一つの口に50 ml の等圧型分液ロートを接続した。等圧型分液ロートには、100 mgのボラン・アンモニア(NH3BH3, 純度90%)を溶解した10 mlの水溶液を入れた。
509 mg of the catalyst obtained by the above method was placed in a 30 ml capacity two-necked flask, a gas burette was connected to one of the necks, and a 50 ml isobaric separatory funnel was connected to the other. In an isobaric separatory funnel, 10 ml of an aqueous solution in which 100 mg of borane / ammonia (NH 3 BH 3 , purity 90%) was dissolved was added.
真空ポンプを用いて系内を排気し、アルゴンガス置換を行い、等圧型分液ロートから二つ口フラスコにボラン・アンモニア水溶液を流し込み、室温において攪拌を続けた。攪拌開始30秒後に94 ml、45秒後に215 ml、60秒後に215 mlのガス放出が観測された。 The system was evacuated using a vacuum pump, purged with argon gas, a borane / ammonia aqueous solution was poured into the two-necked flask from the isobaric separatory funnel, and stirring was continued at room temperature. A gas release of 94 ml after 30 seconds from the start of stirring, 215 ml after 45 seconds, and 215 ml after 60 seconds was observed.
ガスクロマトグラフィ（GC）及び質量分析(MS)を行った結果、放出ガスは水素であることが確認できた。水素放出量は、原料として用いたボラン・アンモニア(NH3BH3)に対して3.0倍モルであった。 As a result of performing gas chromatography (GC) and mass spectrometry (MS), it was confirmed that the released gas was hydrogen. The amount of hydrogen released was 3.0 times the mol of borane / ammonia (NH 3 BH 3 ) used as a raw material.
また、上記した方法で発生した水素ガスをそのまま固体高分子型燃料電池に導入して、燃料電池が作動することを確認した。 Further, it was confirmed that the hydrogen gas generated by the above-described method was directly introduced into the polymer electrolyte fuel cell and the fuel cell was operated.
実施例４
130 mgの硝酸パラジウム(Pd(NO3)2)、3 gのγ-アルミナ(γ-Al2O3)及び10 mlの水(H2O)をフラスコにいれ、室温で１０分間攪拌し、70℃に加熱して、ポンプで減圧して水を蒸発させた。空気中で300℃、５時間焼成した後、試料に水素ガスをフロー(50 ml/min)しながら、250℃、３時間処理した。この処理によって、パラジウム金属がγ-アルミナ上に担持された触媒（パラジウム及びアルミナの合計量中、パラジウム含有率２重量％）を得た。
Example 4
130 mg palladium nitrate (Pd (NO 3 ) 2 ), 3 g γ-alumina (γ-Al 2 O 3 ) and 10 ml water (H 2 O) were placed in a flask and stirred at room temperature for 10 minutes. The mixture was heated to 70 ° C. and reduced in pressure with a pump to evaporate water. After baking in air at 300 ° C. for 5 hours, the sample was treated at 250 ° C. for 3 hours while flowing hydrogen gas (50 ml / min). By this treatment, a catalyst in which palladium metal was supported on γ-alumina (a palladium content of 2% by weight in the total amount of palladium and alumina) was obtained.
上記方法で得られた触媒280 mgを容量30 mlの二つ口フラスコに入れ、その一つの口に
ガスビューレットを接続し、もう一つの口に50 ml の等圧型分液ロートを接続した。等圧型分液ロートには、100 mgのボラン・アンモニア(NH3BH3, 純度90%)を溶解した10 mlの水溶液を入れた。
280 mg of the catalyst obtained by the above method was placed in a 30-ml two-necked flask, a gas burette was connected to one of the necks, and a 50-ml isobaric separatory funnel was connected to the other. In an isobaric separatory funnel, 10 ml of an aqueous solution in which 100 mg of borane / ammonia (NH 3 BH 3 , purity 90%) was dissolved was added.
真空ポンプを用いて系内を排気し、アルゴンガス置換を行い、等圧型分液ロートから二つ口フラスコにボラン・アンモニア水溶液を流し込み、室温において攪拌を続けた。攪拌開始5分後に8 ml、10分後に16 ml、30分後に44 ml、60分後に103 ml、90分後に163 ml、120分後に205 ml、180分後に205 mlのガス放出が観測された。 The system was evacuated using a vacuum pump, purged with argon gas, a borane / ammonia aqueous solution was poured into the two-necked flask from the isobaric separatory funnel, and stirring was continued at room temperature. Out of stirring, 5 ml after 8 minutes, 16 ml after 10 minutes, 44 ml after 30 minutes, 103 ml after 60 minutes, 163 ml after 90 minutes, 205 ml after 120 minutes, 205 ml after 180 minutes and 205 ml after 205 minutes. .
ガスクロマトグラフィ（GC）及び質量分析(MS)を行った結果、放出ガスは水素であることが確認できた。水素放出量は、原料として用いたボラン・アンモニア(NH3BH3)に対して2.9倍モルであった。 As a result of performing gas chromatography (GC) and mass spectrometry (MS), it was confirmed that the released gas was hydrogen. The amount of hydrogen released was 2.9 moles compared to borane / ammonia (NH 3 BH 3 ) used as a raw material.
また、上記した方法で発生した水素ガスをそのまま固体高分子型燃料電池に導入して、燃料電池が作動することを確認した。 Further, it was confirmed that the hydrogen gas generated by the above-described method was directly introduced into the polymer electrolyte fuel cell and the fuel cell was operated.
実施例５
168 mgの硝酸ロジウム(Rh(NO3)2)、3 gのγ-アルミナ(γ-Al2O3)及び10 mlの水(H2O)をフラスコにいれ、室温で１０分間攪拌し、70℃に加熱して、ポンプで減圧して水を蒸発させた。空気中で300℃、５時間焼成した後、試料に水素ガスをフロー(50 ml/min)しながら、250℃、３時間処理した。この処理によって、ロジウム金属がγ-アルミナ上に担持された触媒（ロジウム及びアルミナの合計量中、ロジウム含有率２重量％）を得た。
Example 5
168 mg of rhodium nitrate (Rh (NO 3 ) 2 ), 3 g of γ-alumina (γ-Al 2 O 3 ) and 10 ml of water (H 2 O) were placed in a flask and stirred at room temperature for 10 minutes. The mixture was heated to 70 ° C. and reduced in pressure with a pump to evaporate water. After baking in air at 300 ° C. for 5 hours, the sample was treated at 250 ° C. for 3 hours while flowing hydrogen gas (50 ml / min). By this treatment, a catalyst in which rhodium metal was supported on γ-alumina (rhodium content 2% by weight in the total amount of rhodium and alumina) was obtained.
上記方法で得られた触媒270 mgを容量30 mlの二つ口フラスコに入れ、その一つの口に
ガスビューレットを接続し、もう一つの口に50 ml の等圧型分液ロートを接続した。等圧型分液ロートには、100 mgのボラン・アンモニア(NH3BH3, 純度90%)を溶解した10 mlの水溶液を入れた。
270 mg of the catalyst obtained by the above method was placed in a 30-ml two-necked flask, a gas burette was connected to one of the necks, and a 50-ml isobaric separatory funnel was connected to the other. In an isobaric separatory funnel, 10 ml of an aqueous solution in which 100 mg of borane / ammonia (NH 3 BH 3 , purity 90%) was dissolved was added.
真空ポンプを用いて系内を排気し、アルゴンガス置換を行い、等圧型分液ロートから二つ口フラスコにボラン・アンモニア水溶液を流し込み、室温において攪拌を続けた。攪拌開始15秒後に81 ml、30秒後に122 ml、45秒後に163 ml、60秒後に204 ml、75秒後に215 ml、90秒後に215 ml、120秒後に215 mlのガス放出が観測された。 The system was evacuated using a vacuum pump, purged with argon gas, a borane / ammonia aqueous solution was poured into the two-necked flask from the isobaric separatory funnel, and stirring was continued at room temperature. 81 ml after 15 seconds of stirring, 122 ml after 30 seconds, 163 ml after 45 seconds, 204 ml after 60 seconds, 215 ml after 75 seconds, 215 ml after 90 seconds, 215 ml after 120 seconds, and 215 ml after 120 seconds. .
ガスクロマトグラフィ（GC）及び質量分析(MS)を行った結果、放出ガスは水素であることが確認できた。水素放出量は、原料として用いたボラン・アンモニア(NH3BH3)に対して3.0倍モルであった。 As a result of performing gas chromatography (GC) and mass spectrometry (MS), it was confirmed that the released gas was hydrogen. The amount of hydrogen released was 3.0 times the mol of borane / ammonia (NH 3 BH 3 ) used as a raw material.
さらに等圧型分液ロートから二つ口フラスコに、100 mgのボラン・アンモニア(NH3BH3,
純度90%)を溶解した10 mlの水溶液を追加して流し込み、室温において攪拌を続けた。攪拌開始75秒後に190 ml、90秒後に215 ml、120秒後に215 mlのガス放出が観測された。
Furthermore, 100 mg of borane / ammonia (NH 3 BH 3 ,
An additional 10 ml of an aqueous solution in which 90% purity was dissolved was poured, and stirring was continued at room temperature. A gas release of 190 ml was observed 75 seconds after the start of stirring, 215 ml after 90 seconds, and 215 ml after 120 seconds.
ガスクロマトグラフィ（GC）及び質量分析(MS)を行った結果、放出ガスは水素であることが確認できた。水素放出量は、原料として用いたボラン・アンモニア(NH3BH3)に対して3.0倍モルであった。 As a result of performing gas chromatography (GC) and mass spectrometry (MS), it was confirmed that the released gas was hydrogen. The amount of hydrogen released was 3.0 times the mol of borane / ammonia (NH 3 BH 3 ) used as a raw material.
また、上記した方法で発生した水素ガスをそのまま固体高分子型燃料電池に導入して、燃料電池が作動することを確認した。 Further, it was confirmed that the hydrogen gas generated by the above-described method was directly introduced into the polymer electrolyte fuel cell and the fuel cell was operated.
実施例６
935 mgの硝酸ニッケル(Ni(NO3)2)、3 gのγ-アルミナ(γ-Al2O3)及び10 mlの水(H2O)をフラスコにいれ、室温で30分間攪拌し、90℃に加熱して、ポンプで減圧して水を蒸発させた。空気中で600℃、５時間焼成した後、試料に水素ガスをフロー(50 ml/min)しながら、500℃、５時間処理した。この処理によって、ニッケル金属がγ-アルミナ上に担持された触媒（ニッケル及びアルミナの合計量中、ニッケル含有率１０重量％）を得た。
Example 6
935 mg of nickel nitrate (Ni (NO 3 ) 2 ), 3 g of γ-alumina (γ-Al 2 O 3 ) and 10 ml of water (H 2 O) were placed in a flask and stirred at room temperature for 30 minutes. The mixture was heated to 90 ° C. and reduced in pressure with a pump to evaporate water. After baking in air at 600 ° C. for 5 hours, the sample was treated at 500 ° C. for 5 hours while flowing hydrogen gas (50 ml / min). By this treatment, a catalyst in which nickel metal was supported on γ-alumina (nickel content of 10% by weight in the total amount of nickel and alumina) was obtained.
上記方法で得られた触媒30 mgを容量30 mlの二つ口フラスコに入れ、その一つの口にガスビューレットを接続し、もう一つの口に50 ml の等圧型分液ロートを接続した。等圧型分液ロートには、100 mgのボラン・アンモニア(NH3BH3, 純度90%)を溶解した10 mlの水溶液を入れた。 30 mg of the catalyst obtained by the above method was placed in a two-necked flask with a volume of 30 ml, a gas burette was connected to one of the necks, and a 50 ml isobaric separatory funnel was connected to the other. In an isobaric separatory funnel, 10 ml of an aqueous solution in which 100 mg of borane / ammonia (NH 3 BH 3 , purity 90%) was dissolved was added.
真空ポンプを用いて系内を排気し、アルゴンガス置換を行い、等圧型分液ロートから二つ口フラスコにボラン・アンモニア水溶液を流し込み、室温において攪拌を続けた。攪拌開始30分後に6 ml、60分後に35 ml、90分後に76 ml、150分後に161 ml、180分後に177 ml、210分後に177 mlのガス放出が観測された。 The system was evacuated using a vacuum pump, purged with argon gas, a borane / ammonia aqueous solution was poured into the two-necked flask from the isobaric separatory funnel, and stirring was continued at room temperature. Outgassing of 6 ml 30 minutes after the start of stirring, 35 ml after 60 minutes, 76 ml after 90 minutes, 161 ml after 150 minutes, 177 ml after 180 minutes, and 177 ml after 210 minutes was observed.
ガスクロマトグラフィ（GC）及び質量分析(MS)を行った結果、放出ガスは水素であることが確認できた。水素放出量は、原料として用いたボラン・アンモニア(NH3BH3)に対して2.5倍モルであった。 As a result of performing gas chromatography (GC) and mass spectrometry (MS), it was confirmed that the released gas was hydrogen. The amount of hydrogen released was 2.5 moles compared to borane / ammonia (NH 3 BH 3 ) used as a raw material.
さらに等圧型分液ロートから二つ口フラスコに、100 mgのボラン・アンモニア(NH3BH3,
純度90%)を溶解した10 mlの水溶液を追加して流し込み、室温において攪拌を続けた。攪拌開始10分後に15 ml、30分後に58 ml、60分後に121 ml、90分後に175 ml、100分後に204
ml、110分後に206 mlのガス放出が観測された。
Furthermore, 100 mg of borane / ammonia (NH 3 BH 3 ,
An additional 10 ml of an aqueous solution in which 90% purity was dissolved was poured, and stirring was continued at room temperature. 15 minutes after starting stirring, 58 ml after 30 minutes, 121 ml after 60 minutes, 175 ml after 90 minutes, 204 after 100 minutes
ml, outgassing of 206 ml was observed after 110 minutes.
ガスクロマトグラフィ（GC）及び質量分析(MS)を行った結果、放出ガスは水素であることが確認できた。水素放出量は、原料として用いたボラン・アンモニア(NH3BH3)に対して2.9倍モルであった。 As a result of performing gas chromatography (GC) and mass spectrometry (MS), it was confirmed that the released gas was hydrogen. The amount of hydrogen released was 2.9 moles compared to borane / ammonia (NH 3 BH 3 ) used as a raw material.
また、上記した方法で発生した水素ガスをそのまま固体高分子型燃料電池に導入して、燃料電池が作動することを確認した。 Further, it was confirmed that the hydrogen gas generated by the above-described method was directly introduced into the polymer electrolyte fuel cell and the fuel cell was operated.
実施例７
890 mgの硝酸銅(Cu(NO3)2)、3 gのγ-アルミナ(γ-Al2O3)及び10 mlの水(H2O)をフラスコにいれ、室温で30分間攪拌し、90℃に加熱して、ポンプで減圧して水を蒸発させた。空気中で600℃、５時間焼成した後、試料に水素ガスをフロー(50 ml/min)しながら、500℃
、５時間処理した。この処理によって、銅金属がγ-アルミナ上に担持された触媒（銅及
びアルミナの合計量中、銅含有率１０重量％）を得た。
Example 7
890 mg of copper nitrate (Cu (NO 3 ) 2 ), 3 g of γ-alumina (γ-Al 2 O 3 ) and 10 ml of water (H 2 O) were placed in a flask and stirred at room temperature for 30 minutes. The mixture was heated to 90 ° C. and reduced in pressure with a pump to evaporate water. After calcination in air at 600 ° C for 5 hours, while flowing hydrogen gas (50 ml / min) to the sample,
Treated for 5 hours. By this treatment, a catalyst in which copper metal was supported on γ-alumina (a copper content of 10% by weight in the total amount of copper and alumina) was obtained.
上記方法で得られた触媒35 mgを容量30 mlの二つ口フラスコに入れ、その一つの口にガスビューレットを接続し、もう一つの口に50 ml の等圧型分液ロートを接続した。等圧型分液ロートには、100 mgのボラン・アンモニア(NH3BH3, 純度90%)を溶解した10 mlの水溶
液を入れた。
35 mg of the catalyst obtained by the above method was placed in a 30-ml two-necked flask, a gas burette was connected to one of the necks, and a 50-ml isobaric separatory funnel was connected to the other. In an isobaric separatory funnel, 10 ml of an aqueous solution in which 100 mg of borane / ammonia (NH 3 BH 3 , purity 90%) was dissolved was added.
真空ポンプを用いて系内を排気し、アルゴンガス置換を行い、等圧型分液ロートから二つ口フラスコにボラン・アンモニア水溶液を流し込み、室温において攪拌を続けた。攪拌開始10分後に4 ml、30分後に15 ml、140分後に70 ml、230分後に122 ml、390分後に170 ml、420分後に173 mlのガス放出が観測された。 The system was evacuated using a vacuum pump, purged with argon gas, a borane / ammonia aqueous solution was poured into the two-necked flask from the isobaric separatory funnel, and stirring was continued at room temperature. Outgassing of 4 ml after starting stirring, 15 ml after 30 minutes, 70 ml after 140 minutes, 122 ml after 230 minutes, 170 ml after 390 minutes, and 173 ml after 420 minutes was observed.
ガスクロマトグラフィ（GC）及び質量分析(MS)を行った結果、放出ガスは水素であることが確認できた。水素放出量は、原料として用いたボラン・アンモニア(NH3BH3)に対して2.4 倍モルであった。 As a result of performing gas chromatography (GC) and mass spectrometry (MS), it was confirmed that the released gas was hydrogen. The amount of hydrogen released was 2.4 times the molar amount of borane / ammonia (NH 3 BH 3 ) used as a raw material.
また、上記した方法で発生した水素ガスをそのまま固体高分子型燃料電池に導入して、燃料電池が作動することを確認した。 Further, it was confirmed that the hydrogen gas generated by the above-described method was directly introduced into the polymer electrolyte fuel cell and the fuel cell was operated.
実施例８
930 mgの硝酸コバルトル(Co(NO3)2)、3 gのγ-アルミナ(γ-Al2O3)及び10 mlの水(H2O)をフラスコにいれ、室温で30分間攪拌し、90℃に加熱して、ポンプで減圧して水を蒸発させた。空気中で600℃、５時間焼成した後、試料に水素ガスをフロー(50 ml/min)しながら、500℃、５時間処理した。この処理によって、コバルト金属がγ-アルミナ上に担持された触媒（コバルト及びアルミナの合計量中、コバルト含有率１０重量％）を得た。
Example 8
930 mg of cobalt nitrate (Co (NO 3 ) 2 ), 3 g of γ-alumina (γ-Al 2 O 3 ) and 10 ml of water (H 2 O) were placed in a flask and stirred at room temperature for 30 minutes. The mixture was heated to 90 ° C. and reduced in pressure with a pump to evaporate water. After baking in air at 600 ° C. for 5 hours, the sample was treated at 500 ° C. for 5 hours while flowing hydrogen gas (50 ml / min). By this treatment, a catalyst in which cobalt metal was supported on γ-alumina (cobalt content of 10% by weight in the total amount of cobalt and alumina) was obtained.
上記方法で得られた触媒30 mgを容量30 mlの二つ口フラスコに入れ、その一つの口にガスビューレットを接続し、もう一つの口に50 ml の等圧型分液ロートを接続した。等圧型分液ロートには、100 mgのボラン・アンモニア(NH3BH3, 純度90%)を溶解した10 mlの水溶液を入れた。 30 mg of the catalyst obtained by the above method was placed in a two-necked flask with a volume of 30 ml, a gas burette was connected to one of the necks, and a 50 ml isobaric separatory funnel was connected to the other. In an isobaric separatory funnel, 10 ml of an aqueous solution in which 100 mg of borane / ammonia (NH 3 BH 3 , purity 90%) was dissolved was added.
真空ポンプを用いて系内を排気し、アルゴンガス置換を行い、等圧型分液ロートから二つ口フラスコにボラン・アンモニア水溶液を流し込み、室温において攪拌を続けた。攪拌開始10分後に18 ml、20分後に41 ml、30分後に62 ml、60分後に125 ml、90分後に185 ml
、130分後に207 ml、150分後に207 mlのガス放出が観測された。
The system was evacuated using a vacuum pump, purged with argon gas, a borane / ammonia aqueous solution was poured into the two-necked flask from the isobaric separatory funnel, and stirring was continued at room temperature. 18 minutes after starting stirring, 41 ml after 20 minutes, 62 ml after 30 minutes, 125 ml after 60 minutes, 185 ml after 90 minutes
Outgassing of 207 ml after 130 minutes and 207 ml after 150 minutes was observed.
ガスクロマトグラフィ（GC）及び質量分析(MS)を行った結果、放出ガスは水素であることが確認できた。水素放出量は、原料として用いたボラン・アンモニア(NH3BH3)に対して2.9倍モルであった。 As a result of performing gas chromatography (GC) and mass spectrometry (MS), it was confirmed that the released gas was hydrogen. The amount of hydrogen released was 2.9 moles compared to borane / ammonia (NH 3 BH 3 ) used as a raw material.
さらに等圧型分液ロートから二つ口フラスコに、100 mgのボラン・アンモニア(NH3BH3,
純度90%)を溶解した10 mlの水溶液を追加して流し込み、室温において攪拌を続けた。攪拌開始23分後に60 ml、30分後に80 ml、40分後に112 ml、60分後に170 ml、80分後に210 ml、100分後に210 mlのガス放出が観測された。
Furthermore, 100 mg of borane / ammonia (NH 3 BH 3 ,
An additional 10 ml of an aqueous solution in which 90% purity was dissolved was poured, and stirring was continued at room temperature. Outgassing of 60 ml 23 minutes after starting stirring, 80 ml after 30 minutes, 112 ml after 40 minutes, 170 ml after 60 minutes, 210 ml after 80 minutes, and 210 ml after 100 minutes was observed.
ガスクロマトグラフィ（GC）及び質量分析(MS)を行った結果、放出ガスは水素であることが確認できた。水素放出量は、原料として用いたボラン・アンモニア(NH3BH3)に対して2.9倍モルであった。 As a result of performing gas chromatography (GC) and mass spectrometry (MS), it was confirmed that the released gas was hydrogen. The amount of hydrogen released was 2.9 moles compared to borane / ammonia (NH 3 BH 3 ) used as a raw material.
さらに等圧型分液ロートから二つ口フラスコに、100 mgのボラン・アンモニア(NH3BH3,
純度90%)を溶解した10 mlの水溶液を追加して流し込み、室温において攪拌を続けた。攪拌開始5分後に17 ml、10分後に37 ml、30分後に107 ml、60分後に205 ml、90分後に208 mlのガス放出が観測された。
Furthermore, 100 mg of borane / ammonia (NH 3 BH 3 ,
An additional 10 ml of an aqueous solution in which 90% purity was dissolved was poured, and stirring was continued at room temperature. Outgassing of 17 ml after 5 minutes from the start of stirring, 37 ml after 10 minutes, 107 ml after 30 minutes, 205 ml after 60 minutes, and 208 ml after 90 minutes was observed.
ガスクロマトグラフィ（GC）及び質量分析(MS)を行った結果、放出ガスは水素であるこ
とが確認できた。水素放出量は、原料として用いたボラン・アンモニア(NH3BH3)に対して2.9倍モルであった。
As a result of performing gas chromatography (GC) and mass spectrometry (MS), it was confirmed that the released gas was hydrogen. The amount of hydrogen released was 2.9 moles compared to borane / ammonia (NH 3 BH 3 ) used as a raw material.
また、上記した方法で発生した水素ガスをそのまま固体高分子型燃料電池に導入して、燃料電池が作動することを確認した。 Further, it was confirmed that the hydrogen gas generated by the above-described method was directly introduced into the polymer electrolyte fuel cell and the fuel cell was operated.
実施例９
740 mgの硝酸コバルトル(Co(NO3)2)、2.5 gのシリカ(SiO2)及び10 mlの水(H2O)をフラ
スコにいれ、室温で30分間攪拌し、90℃に加熱して、ポンプで減圧して水を蒸発させた。空気中で600℃、５時間焼成した後、試料に水素ガスをフロー(30 ml/min)しながら、500
℃、3時間処理した。この処理によって、コバルト金属がシリカ上に担持された触媒（コ
バルト及びシリカの合計量中、コバルト含有率9.5重量％）を得た。
Example 9
740 mg of cobalt nitrate (Co (NO 3 ) 2 ), 2.5 g of silica (SiO 2 ) and 10 ml of water (H 2 O) are placed in a flask, stirred for 30 minutes at room temperature and heated to 90 ° C. The water was evaporated by depressurizing with a pump. After calcination in air at 600 ° C for 5 hours, while flowing hydrogen gas (30 ml / min) to the sample,
Treated for 3 hours at ° C. By this treatment, a catalyst in which cobalt metal was supported on silica (cobalt content 9.5% by weight in the total amount of cobalt and silica) was obtained.
上記方法で得られた触媒10.6 mgを容量30 mlの二つ口フラスコに入れ、その一つの口にガスビューレットを接続し、もう一つの口に50 ml の等圧型分液ロートを接続した。等圧型分液ロートには、100 mgのボラン・アンモニア(NH3BH3, 純度90%)を溶解した10 mlの水溶液を入れた。 10.6 mg of the catalyst obtained by the above method was placed in a 30-ml two-necked flask, a gas burette was connected to one of the necks, and a 50-ml isobaric separatory funnel was connected to the other. In an isobaric separatory funnel, 10 ml of an aqueous solution in which 100 mg of borane / ammonia (NH 3 BH 3 , purity 90%) was dissolved was added.
真空ポンプを用いて系内を排気し、アルゴンガス置換を行い、等圧型分液ロートから二つ口フラスコにボラン・アンモニア水溶液を流し込み、室温において攪拌を続けた。攪拌開始10分後に28 ml、16分後に89 ml、20分後に134 ml、24分後に183 ml、30分後に210 ml、40分後に212 mlのガス放出が観測された。 The system was evacuated using a vacuum pump, purged with argon gas, a borane / ammonia aqueous solution was poured into the two-necked flask from the isobaric separatory funnel, and stirring was continued at room temperature. Outgassing of 28 ml at 10 minutes after starting stirring, 89 ml after 16 minutes, 134 ml after 20 minutes, 183 ml after 24 minutes, 210 ml after 30 minutes, and 212 ml after 40 minutes was observed.
ガスクロマトグラフィ（GC）及び質量分析(MS)を行った結果、放出ガスは水素であることが確認できた。水素放出量は、原料として用いたボラン・アンモニア(NH3BH3)に対して3.0倍モルであった。 As a result of performing gas chromatography (GC) and mass spectrometry (MS), it was confirmed that the released gas was hydrogen. The amount of hydrogen released was 3.0 times the mol of borane / ammonia (NH 3 BH 3 ) used as a raw material.
また、上記した方法で発生した水素ガスをそのまま固体高分子型燃料電池に導入して、燃料電池が作動することを確認した。 Further, it was confirmed that the hydrogen gas generated by the above-described method was directly introduced into the polymer electrolyte fuel cell and the fuel cell was operated.
実施例１０
1880 mgの硝酸コバルトル(Co(NO3)2)、6.0 gの中性アルミナ(Al2O3)及び10 mlの水(H2O)をフラスコにいれ、室温で30分間攪拌し、90℃に加熱して、ポンプで減圧して水を蒸発
させた。空気中で600℃、５時間焼成した後、試料に水素ガスをフロー(30 ml/min)しながら、500℃、５時間処理した。この処理によって、コバルト金属が中性アルミナ上に担持
された触媒（コバルト及びアルミナの合計量中、コバルト含有率10重量％）を得た。
Example 10
1880 mg cobalt nitrate (Co (NO 3 ) 2 ), 6.0 g neutral alumina (Al 2 O 3 ) and 10 ml water (H 2 O) were placed in a flask and stirred at room temperature for 30 minutes, And the pressure was reduced with a pump to evaporate the water. After baking in air at 600 ° C. for 5 hours, the sample was treated at 500 ° C. for 5 hours while flowing hydrogen gas (30 ml / min). By this treatment, a catalyst in which cobalt metal was supported on neutral alumina (cobalt content of 10% by weight in the total amount of cobalt and alumina) was obtained.
上記方法で得られた触媒31 mgを容量30 mlの二つ口フラスコに入れ、その一つの口にガスビューレットを接続し、もう一つの口に50 ml の等圧型分液ロートを接続した。等圧型分液ロートには、100 mgのボラン・アンモニア(NH3BH3, 純度90%)を溶解した10 mlの水溶液を入れた。 31 mg of the catalyst obtained by the above method was placed in a two-necked flask with a volume of 30 ml, a gas burette was connected to one of the necks, and a 50 ml isobaric separatory funnel was connected to the other. In an isobaric separatory funnel, 10 ml of an aqueous solution in which 100 mg of borane / ammonia (NH 3 BH 3 , purity 90%) was dissolved was added.
真空ポンプを用いて系内を排気し、アルゴンガス置換を行い、等圧型分液ロートから二つ口フラスコにボラン・アンモニア水溶液を流し込み、室温において攪拌を続けた。攪拌開始25分後に4 ml、60分後に22 ml、120分後に66 ml、150分後に96 ml、220分後に153 ml、250分後に180 ml、290分後に202 ml、300分後に202 mlのガス放出が観測された。 The system was evacuated using a vacuum pump, purged with argon gas, a borane / ammonia aqueous solution was poured into the two-necked flask from the isobaric separatory funnel, and stirring was continued at room temperature. 4 ml after starting stirring, 22 ml after 60 minutes, 66 ml after 120 minutes, 96 ml after 150 minutes, 153 ml after 220 minutes, 180 ml after 250 minutes, 202 ml after 290 minutes, 202 ml after 300 minutes Outgassing was observed.
ガスクロマトグラフィ（GC）及び質量分析(MS)を行った結果、放出ガスは水素であることが確認できた。水素放出量は、原料として用いたボラン・アンモニア(NH3BH3)に対して2.8倍モルであった。 As a result of performing gas chromatography (GC) and mass spectrometry (MS), it was confirmed that the released gas was hydrogen. The amount of hydrogen released was 2.8 times mol of borane / ammonia (NH 3 BH 3 ) used as a raw material.
また、上記した方法で発生した水素ガスをそのまま固体高分子型燃料電池に導入して、燃料電池が作動することを確認した。 Further, it was confirmed that the hydrogen gas generated by the above-described method was directly introduced into the polymer electrolyte fuel cell and the fuel cell was operated.
水素ガス発生試験結果
図１は、実施例２、３及び５の各水素ガス発生試験におけるNH3BH3 (10 ml, 1 wt.%)水溶液からの水素放出量と反応時間との関係を示すグラフである。図１には、更に、比較試験結果として、白金黒(Pt black)、酸化ルテニウム（RuO2）、又はジ-μ-クロロビス(η-シクロオクタ-1,5-ジエン)ロジウム(I) ([Rh(1,5-COD)(μ-Cl)]2)を触媒として用いて同
様の条件で水素発生試験を行ったものを示す。これらの試験では、触媒の金属モル数対NH3BH3モル数の比は同じである。
Results of Hydrogen Gas Generation Test FIG. 1 shows the relationship between the amount of hydrogen released from NH 3 BH 3 (10 ml, 1 wt.%) Aqueous solution and the reaction time in the hydrogen gas generation tests of Examples 2, 3 and 5. It is a graph. In FIG. 1, further, as a result of the comparative test, platinum black (Pt black), ruthenium oxide (RuO 2 ), or di-μ-chlorobis (η-cycloocta-1,5-diene) rhodium (I) ([Rh This shows a hydrogen generation test conducted under the same conditions using (1,5-COD) (μ-Cl)] 2 ) as a catalyst. In these studies, metal molar number The ratio of NH 3 BH 3 moles of catalyst are the same.
図１から明らかなように、実施例２におけるルテニウム担持アルミナ(2 wt% Ru /γ-Al2O3)、実施例３における白金担持アルミナル（2 wt% Pt /γ-Al2O3）、及び実施例５におけるロジウム担持アルミナ(2 wt% Rh /γ-Al2O3)の各触媒を用いた場合には、RuO2、白金黒又は[Rh(1,5-COD)(μ-Cl)]2を触媒とした場合と比較して、短時間で多量の水素を発生
させることができ、各実施例で用いた触媒が、NH3BH3 水溶液からの水素発生反応に対し
て高い活性を有することが判る。
As is clear from FIG. 1, ruthenium-supported alumina in Example 2 (2 wt% Ru / γ-Al 2 O 3 ), platinum-supported alumina in Example 3 (2 wt% Pt / γ-Al 2 O 3 ), And when each catalyst of rhodium supported alumina (2 wt% Rh / γ-Al 2 O 3 ) in Example 5 is used, RuO 2 , platinum black or [Rh (1,5-COD) (μ-Cl )] Compared with the case where 2 is used as a catalyst, a large amount of hydrogen can be generated in a short time, and the catalyst used in each example has high activity for the hydrogen generation reaction from NH 3 BH 3 aqueous solution. It turns out that it has.
図２は、パラジウム担持アルミナ(2 wt% Pd /γ-Al2O3)を触媒として用いた実施例４における水素発生試験と、パラジウム黒(Pd black)を触媒として用いた水素発生試験について、NH3BH3 (10 ml, 1 wt.%)水溶液からの水素放出量と反応時間との関係を示すグラフである。この結果から明らかなように、2 wt% Pd /γ-Al2O3触媒は、パラジウム黒のみからなる触媒と比較して、NH3BH3水溶液からの水素発生反応に対して高い活性を有することが判る。 FIG. 2 shows a hydrogen generation test in Example 4 using palladium-supported alumina (2 wt% Pd / γ-Al 2 O 3 ) as a catalyst and a hydrogen generation test using palladium black (Pd black) as a catalyst. NH 3 BH 3 (10 ml, 1 wt.%) is a graph showing the relationship between the hydrogen release amount and the reaction time from an aqueous solution. As is apparent from this result, the 2 wt% Pd / γ-Al 2 O 3 catalyst has a higher activity for the hydrogen generation reaction from the NH 3 BH 3 aqueous solution than the catalyst composed only of palladium black. I understand that.
図３は、実施例６、７及び８の各水素ガス発生試験で求めたNH3BH3(10 ml, 1 wt.%)水
溶液からの水素放出量と反応時間との関係を示すグラフである。図３から明らかなように、実施例６〜８の各実施例で用いた触媒は、NH3BH3水溶液からの水素発生反応に対して高い活性を示すものであり、特に、ニッケル担持アルミナ(10 wt% Ni /γ-Al2O3)及びコバ
ルト担持アルミナ(10 wt% Co /γ-Al2O3)は、高い活性を有する触媒であった。
FIG. 3 is a graph showing the relationship between the amount of hydrogen released from the NH 3 BH 3 (10 ml, 1 wt.%) Aqueous solution and the reaction time determined in each hydrogen gas generation test of Examples 6, 7 and 8. . As is clear from FIG. 3, the catalysts used in Examples 6 to 8 exhibit high activity for the hydrogen generation reaction from NH 3 BH 3 aqueous solution. 10 wt% Ni / γ-Al 2 O 3 ) and cobalt-supported alumina (10 wt% Co / γ-Al 2 O 3 ) were highly active catalysts.
Claims (4)
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| DE102007038965A1 (en) * | 2007-08-17 | 2009-03-05 | Friedrich-Alexander-Universität Erlangen-Nürnberg | Storage of hydrogen |
| US8377416B2 (en) * | 2008-08-20 | 2013-02-19 | Purdue Research Foundation | Method for releasing hydrogen from ammonia borane |
| EP2352697A1 (en) * | 2008-10-31 | 2011-08-10 | Alliant Techsystems Inc. | Methods and systems for producing hydrogen and system for producing power |
| EP2269253A1 (en) * | 2008-11-12 | 2011-01-05 | Ramot at Tel-Aviv University Ltd. | A direct liquid fuel cell having hydrazine or derivatives thereof as fuel |
| US8038980B2 (en) * | 2009-07-08 | 2011-10-18 | Ford Motor Company | Hydrogen storage materials containing ammonia borane |
| EP3081528A1 (en) | 2015-04-17 | 2016-10-19 | Justus-Liebig-Universität Gießen | Method for release of hydrogen from the adduct of ammonia and borane and use of transition metal free multidentate catalysts for release of hydrogen from the adduct of ammonia and borane |
| CN107930697A (en) * | 2017-11-18 | 2018-04-20 | 桂林电子科技大学 | A kind of 67 composite materials of Pt/ZIF for being used to be catalyzed ammonia borane hydrolysis hydrogen manufacturing |
| CN111167440B (en) * | 2020-01-07 | 2023-05-02 | 郑州大学 | Catalyst for ammonia borane hydrolysis hydrogen evolution and preparation method thereof |
| CN111701592B (en) * | 2020-07-03 | 2022-10-21 | 重庆工商大学 | Co/M II Preparation of Fe layered double hydroxide and ammonia borane hydrogen production |
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