JP2002210367A - Catalyst for purifying hydrogen gas for fuel cell and fuel cell anode catalyst - Google Patents
Catalyst for purifying hydrogen gas for fuel cell and fuel cell anode catalystInfo
- Publication number
- JP2002210367A JP2002210367A JP2001011219A JP2001011219A JP2002210367A JP 2002210367 A JP2002210367 A JP 2002210367A JP 2001011219 A JP2001011219 A JP 2001011219A JP 2001011219 A JP2001011219 A JP 2001011219A JP 2002210367 A JP2002210367 A JP 2002210367A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- fuel cell
- hydrogen gas
- composite oxide
- mno
- 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.)
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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
- Y02E60/50—Fuel cells
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、燃料電池に用いる
触媒に関する。詳しくは燃料電池用水素ガス精製触媒、
及び、燃料電池アノード電極触媒に関する。[0001] The present invention relates to a catalyst used for a fuel cell. Specifically, hydrogen gas purification catalyst for fuel cells,
And a fuel cell anode electrode catalyst.
【０００２】[0002]
【従来の技術】固体高分子燃料電池は比較的低温でも高
電流密度が得られるため、環境対応型自動車として実用
化されつつある燃料電池車移動の電源として期待されて
いる。固体高分子型燃料電池では、燃料として水素ガス
が使用されている。この燃料としての水素ガスの製造方
法には、水素吸蔵合金法、ガソリンの触媒分解、メチル
アルコールの触媒分解方法等が使用されてきた。このう
ち、水素吸蔵合金法では使用する合金が希土類合金のＬ
ａ−Ｎｉ5等であって高価で重いという欠点があり、高
純度の水素ガスは得られるものの、合金の消耗もあり、
水素ガス燃料の価格が高価になってしまう。また、ガソ
リンの触媒分解では、メタノールに比較してガソリンは
水素原子に対して炭素原子量が多く構成されており、水
素を多く作れない欠点がある。中で最も期待されている
のが、触媒で低温分解ができ、取り扱いが容易である、
メタノールの水蒸気改質である。2. Description of the Related Art Since a polymer electrolyte fuel cell can provide a high current density even at a relatively low temperature, it is expected as a power source for moving a fuel cell vehicle which is being put into practical use as an environment-friendly vehicle. In a polymer electrolyte fuel cell, hydrogen gas is used as a fuel. As a method for producing hydrogen gas as a fuel, a hydrogen storage alloy method, catalytic decomposition of gasoline, a catalytic decomposition method of methyl alcohol, and the like have been used. Of these, the alloy used in the hydrogen storage alloy method is rare earth alloy L
a-Ni 5 and the like, which has the disadvantage of being expensive and heavy, and although high-purity hydrogen gas can be obtained, there is also consumption of the alloy,
The price of hydrogen gas fuel becomes expensive. Further, in the catalytic cracking of gasoline, gasoline has a larger amount of carbon atoms than hydrogen atoms as compared with methanol, and thus has a drawback that hydrogen cannot be produced much. The most promising among them is that catalysts can be decomposed at low temperatures and are easy to handle.
It is steam reforming of methanol.
【０００３】しかし、通常、メタノールと水から水素と
二酸化炭素とを含有する水素ガスを次式の反応によって
作り出すが、次式の反応を完全に行うことが実際上困難
なので、水素ガス中に約１％のＣＯが存在してしまう。However, hydrogen gas containing hydrogen and carbon dioxide is usually produced from methanol and water by the following reaction. However, it is practically difficult to completely carry out the reaction of the following formula. 1% of CO will be present.
【０００４】ＣＨ3ＯＨ→ＣＯ＋２Ｈ2−２１．７kcal/m
ol ＣＯ＋Ｈ2Ｏ→ＣＯ2＋Ｈ2＋９．８kcal/mol[0004] CH 3 OH → CO + 2H 2 -21.7 kcal / m
ol CO + H 2 O → CO 2 + H 2 +9.8 kcal / mol
【０００５】水素ガス中にＣＯが１％もあると、１００
℃で燃料電池アノード電極のＰｔ触媒に吸着して機能を
低下させる被毒が起こり、アノード反応である水素の分
解反応を阻害して燃料電池の出力低下を起こし、寿命も
短くなる。固体高分子型燃料電池の場合、許容されるＣ
Ｏ濃度は数ｐｐｍ以下である。燃料電池の出力低下を防
止するため、水素ガスにＯ2を６〜１３％を加えてＣＯ
からＣＯ2に酸化除去することが考えられるが、それで
は、爆発の危険性が生じ、また、温度上昇による電極の
面の温度分布のムラが生じたり、Ｈ2の損失と発生電力
の低下の原因となる。When 1% of CO is contained in hydrogen gas, 100%
At ℃, the poisoning of the anode electrode of the fuel cell adsorbed on the Pt catalyst to deteriorate its function occurs, inhibiting the decomposition reaction of hydrogen, which is an anode reaction, causing a decrease in the output of the fuel cell and shortening the service life. In the case of a polymer electrolyte fuel cell, the allowable C
O concentration is several ppm or less. In order to prevent a decrease in the output of the fuel cell, 6 to 13% of O 2 is added to hydrogen gas to reduce CO 2
Can be considered to be oxidized and removed to CO 2 , but this may cause an explosion, and may cause unevenness of the temperature distribution on the electrode surface due to the rise in temperature, loss of H 2 and reduction of generated power. Becomes
【０００６】ＣＯによる燃料電池電極の被毒の問題は、
ボンベ充填した純水素を使用することで回避することが
できるが、詰め替え等が困難であり、さらに、高圧で危
険性が高いという問題点がある。The problem of poisoning of fuel cell electrodes by CO is as follows.
Although it can be avoided by using pure hydrogen filled in a cylinder, there is a problem that refilling and the like are difficult, and there is a high danger at high pressure.
【０００７】そこで、燃料電池においてＣＯの影響を回
避する方法として、触媒存在下で少量の酸素によって水
素ガス中のＣＯをＣＯ2に酸化して低減するＣＯ選択酸
化方法が試みられている。例えば、特開平９−３０８０
２号公報には、この触媒として白金及びルテニウムから
なる触媒が示されている。Therefore, as a method of avoiding the influence of CO in a fuel cell, a CO selective oxidation method of oxidizing and reducing CO in hydrogen gas to CO 2 with a small amount of oxygen in the presence of a catalyst has been attempted. For example, Japanese Patent Application Laid-Open No. 9-3080
No. 2 discloses a catalyst comprising platinum and ruthenium as this catalyst.
【０００８】特開平９−３０８０２号公報では、触媒製
造上のルテニウムの出発物質としては、塩化ルテニウム
水溶液（ＲｕＣｌ3・３Ｈ2Ｏ）を使用している。しか
し、これは製造工程で、触媒の経時変化等の原因となる
Ｃｌの除去が困難である。これに替わるものとして、
［Ｒｕ（ＳＯ3）（ＮＨ3）5］・２Ｈ2Ｏ，Ｒｕ2（ＣＨ3
ＣＯ2）4（ＯＨ）2，［Ｒｕ3Ｏ2（ＮＨ3）14］（Ｎ
Ｏ3）7等があるが、いずれも不安定で製造も容易ではな
い。また、ＲｕＯ4は、揮発性で有毒であるという、問
題点を有している。In Japanese Patent Application Laid-Open No. 9-30802, a ruthenium chloride aqueous solution (RuCl 3 .3H 2 O) is used as a ruthenium starting material for producing a catalyst. However, this is difficult in a manufacturing process to remove Cl which causes a change with time of the catalyst. As an alternative,
[Ru (SO 3 ) (NH 3 ) 5 ] .2H 2 O, Ru 2 (CH 3
CO 2 ) 4 (OH) 2 , [Ru 3 O 2 (NH 3 ) 14 ] (N
O 3 ) 7 etc., but all are unstable and the production is not easy. Further, RuO 4 has a problem that it is volatile and toxic.
【０００９】また、ＣＯとＨ2は分子の大きさ、分子燃
焼熱等も近い値にあり、簡単に分離することは不可能で
ある。Ｐｔ／Ａｌ2Ｏ3触媒ではＨ2は常温で吸着燃焼さ
れ、ＣＯは８０〜１００℃から吸着燃焼される。また、
Ｐｄ膜は、Ｈ2のみ透過する性質があるが、相当の圧力
を加える必要がある。このように、燃料電池用水素ガス
中のＣＯの選択酸化は困難であった。Further, CO and H 2 have similar values in terms of molecular size, molecular combustion heat, and the like, and cannot be easily separated. In the Pt / Al 2 O 3 catalyst, H 2 is adsorbed and combusted at room temperature, and CO is adsorbed and combusted from 80 to 100 ° C. Also,
The Pd film has the property of permeating only H 2, but requires considerable pressure. Thus, it was difficult to selectively oxidize CO in hydrogen gas for fuel cells.
【００１０】また、燃料電池のアノード電極自体をＣＯ
に被毒されないものとするための開発、研究も行われて
いて、例えば、特開平９−１６１８１１号公報には電極
触媒をＰｔ−Ｆｅ−Ｒｈ等の合金とすることが提案され
ている。しかし、これらもＣＯの被毒を完全に除去でき
るものではない。Further, the anode electrode of the fuel cell is replaced with CO.
Development and research are also being carried out to prevent poisoning. For example, Japanese Patent Application Laid-Open No. 9-161811 proposes that the electrode catalyst be an alloy such as Pt-Fe-Rh. However, these methods also cannot completely remove CO poisoning.
【００１１】[0011]
【発明が解決しようとする課題】本発明は、従来の燃料
電池用水素ガス精製触媒及び燃料電池電極自体のＣＯ被
毒の問題点を解決し、高濃度のＣＯを含む燃料電池用水
素ガス中のＣＯを選択的に酸化除去し、燃料電池用に許
容される水素ガスを精製する触媒、並びに、ＣＯに被毒
されない燃料電池のアノード電極触媒を提供することを
目的とする。SUMMARY OF THE INVENTION The present invention solves the problems of the conventional hydrogen gas purification catalyst for a fuel cell and the CO poisoning of the fuel cell electrode itself. It is an object of the present invention to provide a catalyst for selectively oxidizing and removing CO to purify hydrogen gas permitted for a fuel cell and an anode electrode catalyst for a fuel cell which is not poisoned by CO.
【００１２】[0012]
【課題を解決するための手段】本発明は、ＭｎＯ2、Ｃ
ｏ3Ｏ4、２ＣｕＯ・Ｃｒ2Ｏ3、及び、Ａｇ2Ｏを含む複
合酸化物の表面にＰｔ-ブラック粒子を分散させたこと
を特徴とする燃料電池用水素ガス精製触媒である。さら
に、ＭｎＯ2、Ｃｏ3Ｏ4、及び、ＣｕＯを含む複合酸化
物の表面にＡｇ2Ｏを分散させ、該Ａｇ2Ｏの上からＰｔ
-ブラック粒子層を形成したことを特徴とする燃料電池
アノード電極触媒である。According to the present invention, MnO 2 , C
o 3 O 4, 2CuO · Cr 2 O 3, and a hydrogen gas purification catalyst for a fuel cell, characterized in that the Pt- black particles to the surface of the composite oxide was dispersed containing Ag 2 O. Further, Ag 2 O is dispersed on the surface of the composite oxide containing MnO 2 , Co 3 O 4 , and CuO, and Pt is added from above the Ag 2 O.
-A fuel cell anode electrode catalyst comprising a black particle layer.
【００１３】[0013]
【発明の実施の形態】本発明の燃料電池用水素ガス精製
触媒は、ＣＯとＨ2の共存ガスにおいて、ＣＯをＣＯ2に
酸化するが、Ｈ2は酸化しない、ＣＯ選択酸化触媒から
なるものである。Fuel cell hydrogen gas purifying catalyst of the embodiment of the present invention, in the coexistence gases CO and H 2, is to oxidize CO to CO 2, H 2 does not oxidize, made of CO selective oxidation catalyst It is.
【００１４】不完全燃焼警報用に使用するＣＯセンサー
であって、ＣＯとＨ2（但し５００ｐｐｍ）の共存ガス
中からＣＯのみ選択的に検知できるセンサーに使用され
るＣＯ選択酸化触媒は、金属の中で、ＣＯの酸化特性に
関して、低温感度、相対感度ともＰｔが最も高いことに
基づいて作成されている。Ｐｔを主触媒とした、担持貴
金属触媒とする場合には、ＣＯに対する感度が高く、低
温活性があり、かつ化学的に安定で、比較的被毒に強い
Ｐｔ−ブラック／Ａｌ2Ｏ3が一般に使用される。しか
し、Ｐｔ−ブラック／Ａｌ2Ｏ3はＣＯと同様な感度をＨ
2に対しても有している。A CO selective oxidation catalyst used for a CO sensor used for an incomplete combustion warning and capable of selectively detecting only CO from a coexisting gas of CO and H 2 (500 ppm) is a metal catalyst. Among them, the oxidation characteristics of CO are created based on the fact that Pt is the highest in both low-temperature sensitivity and relative sensitivity. In the case of using a supported noble metal catalyst having Pt as a main catalyst, Pt-black / Al 2 O 3 which has high sensitivity to CO, has low-temperature activity, is chemically stable, and is relatively resistant to poisoning is generally used. used. However, Pt-black / Al 2 O 3 has the same sensitivity as CO as H
Has also for two .
【００１５】ＣＯセンサー用触媒は、Ｈ2感度を除去す
るために、ＭｎＯ2、２ＣｕＯ・Ｃｒ 2Ｏ3、Ｃｏ3Ｏ4、
ＡｇＯ、及びγ−Ａｌ2Ｏ3を含む金属酸化物をＰｔ−ブ
ラックと組み合わせて触媒としている。このうち、Ｍｎ
Ｏ2は結晶成長抑制をする。ＣｕＯはＨ2感度の除去を行
うが、ＣｕＯのみでは酸化還元に弱いため、Ｃｒ2Ｏ3で
安定化する。Ｃｏ3Ｏ4とＭｎＯ2はＡｇ2ＯにＯ2-を供給
し、Ｈ2感度除去の補助をする。γ−Ａｌ2Ｏ3は、線材
への熱伝導及び触媒保持体の働きをする。ＣＯセンサー
の触媒のセンサーは、センサー温度、すなわち、触媒温
度を１５０〜１６０℃に保つ様、センサーのコイル形状
と抵抗値を加工（ブリッジ電圧：ＤＣ６．０Ｖ）し、５
００ｐｐｍのＣＯ、Ｈ2ガスに接触し、燃焼した時の温
度を検出し、電圧に変換して各々ＣＯ：２０〜２５ｍ
Ｖ，Ｈ2：０ｍＶの出力が得られる様、設計されてい
る。The catalyst for the CO sensor is HTwoEliminate sensitivity
MnOTwo、 2CuO ・ Cr TwoOThree, CoThreeOFour,
AgO and γ-AlTwoOThreePt-b
The catalyst is used in combination with a rack. Of these, Mn
OTwoSuppresses crystal growth. CuO is HTwoRemove sensitivity
However, since CuO alone is vulnerable to oxidation and reduction,TwoOThreeso
Stabilize. CoThreeOFourAnd MnOTwoIs AgTwoO to O2-Supply
And HTwoHelps remove sensitivity. γ-AlTwoOThreeIs a wire rod
It acts as a heat conductor and catalyst support. CO sensor
The catalyst sensor has a sensor temperature,
Sensor coil shape to keep the temperature between 150 and 160 ° C
And the resistance value (bridge voltage: DC 6.0 V)
00 ppm CO, HTwoThe temperature at which the gas contacts and burns
The degree is detected and converted into a voltage, and CO: 20 to 25 m, respectively.
V, HTwo: Designed to obtain 0 mV output
You.
【００１６】本発明は、ＭｎＯ2、Ｃｏ3Ｏ4、２ＣｕＯ
・Ｃｒ2Ｏ3、及び、Ａｇ2Ｏを含む複合酸化物の表面に
Ｐｔ-ブラックを分散させた触媒であって、燃料電池用
水素ガス中のＣＯのみを選択的に酸化して、水素ガスを
精製する触媒である。当該触媒からなる触媒層に、例え
ば、メタノールの水蒸気改質によって得られた水素ガス
を適切な設定温度と上限制御温度の下で導入すると、Ｃ
Ｏは酸化されるがＨ2は酸化されず、当初約１％の濃度
のＣＯが含まれる水素ガスは、固体高分子型燃料電池の
場合に許容されるＣＯ濃度にすることができる。The present invention relates to MnO 2 , Co 3 O 4 , 2CuO
A catalyst in which Pt-black is dispersed on the surface of a composite oxide containing Cr 2 O 3 and Ag 2 O, and selectively oxidizes only CO in hydrogen gas for a fuel cell to produce hydrogen gas Is a catalyst for purifying When, for example, hydrogen gas obtained by steam reforming of methanol is introduced into a catalyst layer made of the catalyst at an appropriate set temperature and an upper limit control temperature, C
O is oxidized H 2 is not oxidized, the hydrogen gas that contains CO originally about 1% concentration can be CO concentrations that are acceptable in the case of a polymer electrolyte fuel cell.
【００１７】本発明の燃料電池用水素ガス精製触媒の複
合酸化物には、使用される触媒層の形状、及び精製条件
等に応じて、適切な量のγ−Ａｌ2Ｏ3を保持体として含
むことができる。The composite oxide of the hydrogen gas purifying catalyst for a fuel cell according to the present invention contains an appropriate amount of γ-Al 2 O 3 as a support in accordance with the shape of the catalyst layer to be used and the purification conditions. Can be included.
【００１８】複合酸化物の卑金属の組成は限定されるも
のではないが、ＭｎＯ2が３０〜５５重量％、２ＣｕＯ
・Ｃｒ2Ｏ3が１５〜３５重量％、Ｃｏ3Ｏ4が５〜２５重
量％γ−Ａｌ2Ｏ3が１０〜３０重量％であると、触媒の
選択性、及び安定性等が優れ好ましい。当該卑金属及
び、微量のＡｇ2Ｏを含む混合物は球形粒状、円柱形ペ
レット状等の好ましい形状に形成される。Although the composition of the base metal of the composite oxide is not limited, the content of MnO 2 is 30 to 55% by weight,
When the content of Cr 2 O 3 is 15 to 35% by weight, the content of Co 3 O 4 is 5 to 25% by weight, and the content of γ-Al 2 O 3 is 10 to 30% by weight, the selectivity and stability of the catalyst are excellent and preferable. . The mixture containing the base metal and a small amount of Ag 2 O is formed into a preferable shape such as a spherical particle or a cylindrical pellet.
【００１９】成形された複合酸化物の表面にＰｔ−ブラ
ックを分散させて、燃料電池用水素ガス精製触媒が製造
される。By dispersing Pt-black on the surface of the formed composite oxide, a hydrogen gas purification catalyst for a fuel cell is manufactured.
【００２０】触媒製造に係る総ての出発物質は、経時変
化の原因となり、製造工程で除去不可能な、アルカリ金
属、アルカリ土類金属、ハロゲン元素、硫酸塩、及び燐
酸塩を含まないことが必要とされる。従って、形成され
る触媒中にハロゲン等を含ませないため、Ｐｔの出発物
質は［Ｐｔ（ＮＨ3）4］（ＮＯ3）2が好ましい。複合酸
化物の表面にＰｔ−ブラックを分散させる方法は、特に
限定は無く、例えば、［Ｐｔ（ＮＨ3）4］（ＮＯ3）2溶
液を成形された複合酸化物の表面に塗布、乾燥、分解す
る方法が挙げられる。All starting materials involved in the preparation of the catalyst must be free of alkali metals, alkaline earth metals, halogen elements, sulfates, and phosphates that can cause aging and cannot be removed during the manufacturing process. Needed. Therefore, the starting catalyst for Pt is preferably [Pt (NH 3 ) 4 ] (NO 3 ) 2 , because halogens and the like are not contained in the formed catalyst. The method of dispersing Pt-black on the surface of the composite oxide is not particularly limited. For example, a [Pt (NH 3 ) 4 ] (NO 3 ) 2 solution is applied to the surface of the formed composite oxide, dried, Decomposition method is mentioned.
【００２１】また、ＭｎＯ2、Ｃｏ3Ｏ4、及び、ＣｕＯ
を含む複合酸化物の表面にＡｇ2Ｏを分散し、その上に
Ｐｔ-ブラック層を形成した触媒は、ＣＯとＨ2の混合ガ
スにおいてＨ2のみを選択的に吸着酸化する。当該触媒
を燃料電池アノード電極触媒として使用すると、当該触
媒にはＣＯが吸着しないため、Ｈ2→２Ｈ+＋ｅ-のアノ
ード反応を、ＣＯを含むＨ2ガスを燃料とした場合に
も、長期間安定的に行うことができる。Further, MnO 2 , Co 3 O 4 and CuO
Dispersed Ag 2 O on the surface of the composite oxide containing, catalyst to form a Pt- black layer thereon, selectively adsorbs oxidized only H 2 in the mixed gas of CO and H 2. When the catalyst is used as a fuel cell anode electrode catalyst, CO is not adsorbed on the catalyst. Therefore, even when H 2 gas containing CO is used as fuel, the anode reaction of H 2 → 2H + + e − can be performed for a long time. It can be performed stably.
【００２２】[0022]
【実施例】以下、本発明を実施例により具体的に説明す
る。しかし、これらの実施例は本発明の実施態様を具体
的に説明するものであり、本発明の範囲を限定するもの
ではない。The present invention will be described below in more detail with reference to examples. However, these examples specifically illustrate embodiments of the present invention and do not limit the scope of the present invention.
【００２３】実施例１ ＭｎＯ2 ４２重量％ ２ＣｕＯ・Ｃｒ2Ｏ3 ２５重量％ Ｃｏ3Ｏ4 １３重量％ γ−Ａｌ2Ｏ3 ２０重量％ 上記組成の混合物に、当該混合物１ｇ当たり５×１０-4
ｇのＡｇＯを加えボールミルにかけて、混合粉砕した
後、直径３．０ｍｍ、長さ３ｍｍの円柱形ペレットに成
型し、［Ｐｔ（ＮＨ3）4］（ＮＯ3）2（１：６０）溶液
をペレット１ｃｍ 2あたり１〜２ｃｃを表面に塗布し、
乾燥後、熱分解して、表面にＰｔ−ブラックを分散さ
せ、水洗乾燥して触媒を得た。Example 1 MnOTwo 42% by weight 2CuO.CrTwoOThree 25% by weight CoThreeOFour 13% by weight γ-AlTwoOThree 20% by weight A mixture of the above composition was added in an amount of 5 × 10-Four
g of AgO was added, and the mixture was mixed and pulverized with a ball mill.
Then, it is formed into a cylindrical pellet of 3.0 mm in diameter and 3 mm in length.
And type [Pt (NHThree)Four] (NOThree)Two(1:60) solution
The pellet 1cm TwoApply 1 to 2 cc per surface to
After drying, it is thermally decomposed and Pt-black is dispersed on the surface.
And washed with water and dried to obtain a catalyst.
【００２４】この触媒は、１２０℃からＣＯを酸化する
性能が有り、ＣＯとＨ2のバランスは１５０〜１６０℃
の間でとれる様になっている。ＣＯセンサに用いると、
センサー温度が１５０℃でＣＯ：１０００ｐｐｍ ３０
〜４０ｍＶ、Ｈ2：１０００ｐｐｍ ０ｍＶの様な特性
が予測される。ＣＯ ０．１％（１０００ｐｐｍ）が燃
焼すると、触媒の温度上昇は９．２℃であるので、設定
温度１５０〜１６０℃、上昇制限温度１６０〜１７０℃
の温度範囲でＣＯを含むＨ2ガスを流せば、ＣＯのみ酸
化されＨ2は酸化されない。出力３ＫＷ燃料電池に必要
なＨ2供給量は、約７５Ｌ／Ｍｉｎであるので、必要量
に応じた触媒層を設計する。This catalyst has a performance of oxidizing CO from 120 ° C., and the balance between CO and H 2 is 150 to 160 ° C.
Between the two. When used for a CO sensor,
CO: 1000 ppm 30 when the sensor temperature is 150 ° C
Characteristics such as ４０40 mV and H 2 : 1000 ppm 0 mV are expected. When 0.1% (1000 ppm) of CO is burned, the temperature rise of the catalyst is 9.2 ° C.
When H 2 gas containing CO is flowed in the temperature range, only CO is oxidized and H 2 is not oxidized. Since the supply amount of H 2 required for a 3 KW fuel cell output is about 75 L / Min, the catalyst layer is designed according to the required amount.
【００２５】実施例２ ＭｎＯ2 ５０重量％ ＣｕＯ ３０重量％ Ｃｏ3Ｏ4 １５重量％ 上記組成の酸化物を含む塗装液を調整し、カーボンに塗
装した。低温乾燥及び１２０℃で２時間乾燥した後、５
００℃で１５〜２０分焼成して複合酸化物を得た。Ａｇ
2Ｏが触媒において０．５重量％になるように、ＡｇＮ
Ｏ3溶液を塗布乾燥させＡｇ2Ｏ層を形成した。［Ｐｔ
（ＮＨ3）4］（ＮＯ3）2（１：６０)溶液をＡｇ2Ｏ層の
上から塗布し、乾燥後、５００℃で分解し、Ｐｔ−ブラ
ックを触媒１ｇ当たり１×１０-4ｇとなる様に分散形成
して、燃料電池のアノード電極触媒を得た。Example 2 50% by weight of MnO 2 30% by weight of CuO 15% by weight of Co 3 O 4 A coating solution containing an oxide having the above composition was prepared and coated on carbon. After drying at low temperature and drying at 120 ° C for 2 hours, 5
The composite oxide was obtained by firing at 00 ° C. for 15 to 20 minutes. Ag
AgN so that 2 O is 0.5% by weight in the catalyst.
The O 3 solution was applied and dried to form an Ag 2 O layer. [Pt
(NH 3 ) 4 ] (NO 3 ) 2 (1:60) solution was applied on the Ag 2 O layer, dried and decomposed at 500 ° C. to remove Pt-black at 1 × 10 -4 g per gram of catalyst. Thus, an anode electrode catalyst for a fuel cell was obtained.
【００２６】[0026]
【発明の効果】本発明の水素ガス精製触媒を用いて精製
された水素ガスにより、燃料電池はＰｔ電極の被毒が無
く、室温で稼働することができ、発電能力も大きくとれ
る。また、本発明のアノード電極触媒によれば、高濃度
ＣＯを含む水素ガスを燃料としてもＣＯによる被毒の無
い燃料電池アノード電極を作成することができる。According to the hydrogen gas purified by using the hydrogen gas purification catalyst of the present invention, the fuel cell can be operated at room temperature without poisoning of the Pt electrode, and the power generation capacity can be increased. Further, according to the anode electrode catalyst of the present invention, a fuel cell anode electrode free from poisoning by CO can be produced even when hydrogen gas containing high concentration CO is used as fuel.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） ５Ｈ０２７ (71)出願人 501130969 早川 孝 茨城県つくば市東１−１ 経済産業省産業 技術総合研究所物質工学工業技術研究所内 (71)出願人 501131106 折田 秀夫 茨城県つくば市東１−１ 経済産業省産業 技術総合研究所物質工学工業技術研究所内 (72)発明者 森 冨久男 千葉県松戸市河原塚423−７ (72)発明者 水上 富士夫 茨城県つくば市東１−１ 経済産業省産業 技術総合研究所物質工学工業技術研究所内 (72)発明者 早川 孝 茨城県つくば市東１−１ 経済産業省産業 技術総合研究所物質工学工業技術研究所内 (72)発明者 折田 秀夫 茨城県つくば市東１−１ 経済産業省産業 技術総合研究所物質工学工業技術研究所内 Ｆターム(参考） 4G040 FA06 FB04 FC07 FE01 4G069 AA03 AA08 BA01A BA01B BA08B BB06A BB06B BC31A BC31B BC32A BC32B BC58A BC58B BC62A BC62B BC67A BC67B BC75A BC75B CC32 DA06 EA02Y EE06 EE08 FA01 FA02 FB23 4G140 FA06 FB04 FC07 FE01 5H018 AA06 AS02 BB01 BB06 BB08 BB11 BB13 EE03 EE12 5H026 AA06 EE02 EE12 5H027 AA06 BA17 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification FI FI Theme Court II (Reference) 5H027 (71) Applicant 501130969 Takashi Hayakawa 1-1 Higashi Tsukuba, Ibaraki Pref. Within the Technical Research Institute (71) Applicant 501131106 Hideo Orita 1-1, Higashi 1-1, Tsukuba, Ibaraki Pref. ) Inventor Fujio Mizukami 1-1, Higashi, Tsukuba, Ibaraki Pref., Ministry of Economy, Trade and Industry, National Institute of Advanced Industrial Science and Technology (72) Inventor Takashi Hayakawa 1-1, Higashi, Tsukuba, Ibaraki, Japan Within the Institute of Industrial Technology (72) Inventor Hideo Orita 1-1, Higashi 1-1, Tsukuba City, Ibaraki Prefecture F-term (Reference) 4G040 FA06 FB04 FC07 FE01 4G069 AA03 AA08 BA01A BA01B BA08B BB06A BB06B BC31A BC31B BC32A BC32B BC58A BC58B BC62A BC62B BC67A BC67B BC75 FA BC02EA06 FA06 FB04 FC07 FE01 5H018 AA06 AS02 BB01 BB06 BB08 BB11 BB13 EE03 EE12 5H026 AA06 EE02 EE12 5H027 AA06 BA17
Claims (3)
3、及び、Ａｇ2Ｏを含む複合酸化物の表面にＰｔ-ブラ
ックを分散させたことを特徴とする燃料電池用水素ガス
精製触媒。1. MnO 2 , Co 3 O 4 , 2CuO.Cr 2 O
3. A hydrogen gas purification catalyst for a fuel cell, wherein Pt-black is dispersed on the surface of a composite oxide containing Ag 2 O.
項１記載の燃料電池用水素ガス精製触媒。2. The hydrogen gas purifying catalyst for a fuel cell according to claim 1, wherein the composite oxide further contains Al 2 O 3 .
む複合酸化物の表面にＡｇ2Ｏを分散し、該Ａｇ2Ｏ層の
上にＰｔ-ブラック層を形成させたことを特徴とする燃
料電池アノード電極触媒。Wherein MnO 2, Co 3 O 4 and, characterized by dispersing the Ag 2 O on the surface of the composite oxide containing CuO, to form a Pt- black layer on the Ag 2 O layer Fuel cell anode electrode catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001011219A JP2002210367A (en) | 2001-01-19 | 2001-01-19 | Catalyst for purifying hydrogen gas for fuel cell and fuel cell anode catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001011219A JP2002210367A (en) | 2001-01-19 | 2001-01-19 | Catalyst for purifying hydrogen gas for fuel cell and fuel cell anode catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002210367A true JP2002210367A (en) | 2002-07-30 |
Family
ID=18878380
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001011219A Pending JP2002210367A (en) | 2001-01-19 | 2001-01-19 | Catalyst for purifying hydrogen gas for fuel cell and fuel cell anode catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002210367A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003079470A1 (en) * | 2002-03-20 | 2003-09-25 | Matsushita Electric Industrial Co., Ltd. | Fuel cell |
| JP2006116475A (en) * | 2004-10-22 | 2006-05-11 | Sakaguchi Giken:Kk | Carbon monoxide-removing catalyst, carbon monoxide-removing method, and fuel for fuel battery |
| JP2007111695A (en) * | 2005-10-21 | 2007-05-10 | Samsung Sdi Co Ltd | Oxidation catalyst for carbon monoxide and its production method, fuel processor and fuel cell system |
-
2001
- 2001-01-19 JP JP2001011219A patent/JP2002210367A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003079470A1 (en) * | 2002-03-20 | 2003-09-25 | Matsushita Electric Industrial Co., Ltd. | Fuel cell |
| JP2006116475A (en) * | 2004-10-22 | 2006-05-11 | Sakaguchi Giken:Kk | Carbon monoxide-removing catalyst, carbon monoxide-removing method, and fuel for fuel battery |
| JP2007111695A (en) * | 2005-10-21 | 2007-05-10 | Samsung Sdi Co Ltd | Oxidation catalyst for carbon monoxide and its production method, fuel processor and fuel cell system |
| US8101542B2 (en) | 2005-10-21 | 2012-01-24 | Samsung Sdi Co., Ltd. | Catalyst for oxidizing monoxide and method of preparing the same |
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