JP2001278601A - Reformer for fuel cell - Google Patents
Reformer for fuel cellInfo
- Publication number
- JP2001278601A JP2001278601A JP2000093729A JP2000093729A JP2001278601A JP 2001278601 A JP2001278601 A JP 2001278601A JP 2000093729 A JP2000093729 A JP 2000093729A JP 2000093729 A JP2000093729 A JP 2000093729A JP 2001278601 A JP2001278601 A JP 2001278601A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen separation
- separation tube
- alloy
- reformer
- melting point
- 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.)
- Granted
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
- Y02E60/50—Fuel cells
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、メタノール等の炭
化水素系の燃料ガスを改質して水素ガスを発生させ、燃
料電池へその水素ガスを供給する燃料電池用改質器に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fuel cell reformer for reforming a hydrocarbon fuel gas such as methanol to generate hydrogen gas and supplying the hydrogen gas to a fuel cell.
【０００２】[0002]
【従来の技術】従来の燃料電池用改質器（以下、改質器
という）の一例の基本構成を図３に示す。同図におい
て、１は改質器の筒状の外囲器、２は外囲器１の内部に
設置された改質反応炉としての筒状の炉体であり、その
内部の下端部にはメターノールの燃焼反応，水蒸気改質
反応，部分酸化改質反応等が発生する温度（２００〜６
００℃）に加熱するためのバーナ（燃焼器）５が設置さ
れ、また炉体２の内部には、多数の水素分離管３が周囲
に改質触媒４が充填された状態で、筒状の炉体２の中心
軸方向に略平行に配置されている。この水素分離管３
は、下端が開口され上端が閉じられた筒状の形状であ
る。2. Description of the Related Art FIG. 3 shows a basic structure of an example of a conventional fuel cell reformer (hereinafter, referred to as a reformer). In the figure, reference numeral 1 denotes a cylindrical envelope of a reformer, 2 denotes a cylindrical furnace body as a reforming reaction furnace installed inside the envelope 1, and a lower end portion inside thereof. Temperature at which combustion reaction of methanol, steam reforming reaction, partial oxidation reforming reaction, etc. occur (200 to 6)
A burner (combustor) 5 for heating to a temperature of about 00 ° C.) is provided. Inside the furnace body 2, a large number of hydrogen separation tubes 3 are filled with a reforming catalyst 4, and a cylindrical shape is formed. It is arranged substantially parallel to the central axis direction of the furnace body 2. This hydrogen separation tube 3
Has a cylindrical shape with a lower end opened and an upper end closed.
【０００３】このような改質器は以下のように機能す
る。都市ガス，改質排ガス等を含む燃焼用の燃料ガスお
よび空気が供給されて燃焼するバーナ５により、炉体２
を所定の温度（２００〜６００℃）に加熱する。そし
て、外部より炉体２の内部にメタノール（ＣＨ3ＯＨ）
および水蒸気（Ｈ2Ｏ）を供給すると、以下のような反
応が生じる。 メタノールの燃焼反応（ＣＨ3ＯＨ＋３／２Ｏ2→ＣＯ2
＋２Ｈ2Ｏ） メタノールの水蒸気改質反応（ＣＨ3ＯＨ＋Ｈ2Ｏ→ＣＯ
2＋３Ｈ2） ［３］メタノールの部分酸化改質反応（ＣＨ3ＯＨ＋１
／２Ｏ2→ＣＯ2＋２Ｈ2）である。[0003] Such a reformer functions as follows. The burner 5 is supplied with combustion fuel gas and air including city gas, reformed exhaust gas and the like, and burns.
Is heated to a predetermined temperature (200 to 600 ° C.). Then, methanol (CH 3 OH) is introduced into the furnace body 2 from the outside.
And the supply of water vapor (H 2 O), the following reaction occurs. Methanol combustion reaction (CH 3 OH + 3 / 2O 2 → CO 2
+ 2H 2 O) Steam reforming reaction of methanol (CH 3 OH + H 2 O → CO
2 + 3H 2 ) [3] Partial oxidation reforming reaction of methanol (CH 3 OH + 1
/ 2O 2 → CO 2 + 2H 2 ).
【０００４】上記［２］の反応は２００〜３００℃で、
［３］の反応は４００〜６００℃で、［２］および
［３］の併用反応は２００〜６００℃でそれぞれ生じ
る。また、改質後の改質ガス中には一酸化炭素が含まれ
ており、以下の反応により一酸化炭素から水素ガスを発
生させることもできる。 ［４］一酸化炭素の変成（シフト）反応（ＣＯ＋Ｈ2Ｏ
→ＣＯ2＋Ｈ2）である。The above reaction [2] is carried out at 200 to 300 ° C.
The reaction [3] occurs at 400 to 600 ° C, and the combined reaction of [2] and [3] occurs at 200 to 600 ° C. In addition, the reformed gas after reforming contains carbon monoxide, and hydrogen gas can be generated from carbon monoxide by the following reaction. [4] Carbon monoxide shift reaction (CO + H 2 O)
→ CO 2 + H 2 ).
【０００５】そして、図４に示すように、改質ガス中に
含まれるＨ2，ＣＯ2，ＣＯ，Ｈ2ＯのうちＨ2のみが、多
孔質の水素分離管３の壁を通過してその内部に侵入し、
水素リッチのガスとして外部に排出され、燃料電池へ供
給される。As shown in FIG. 4, only H 2 of H 2 , CO 2 , CO and H 2 O contained in the reformed gas passes through the wall of the porous hydrogen separation tube 3. Penetrate into it,
It is discharged to the outside as a hydrogen-rich gas and supplied to the fuel cell.
【０００６】この水素分離管３は、多孔質のジルコニア
セラミックス、所謂Ｙ2Ｏ3を約８ｍｏｌ％ドープした安
定化ジルコニア（ＹＳＺ）セラミックス等から成り、図
２に示すように、その表面には改質反応の触媒としての
Ｐｄ合金であるＡｇ−Ｐｄ層３ａが厚膜印刷法等により
被着されている。そして、水素分離管３の下端部は、Ｆ
ｅ−Ｎｉ−Ｃｏ合金等から成る筒状で金属製の固定部材
６に挿入され、前記下端部の外周面が封着用ガラス７を
介して接合されていた。The hydrogen separation tube 3 is made of a porous zirconia ceramic, so-called stabilized zirconia (YSZ) ceramic doped with about 8 mol% of Y 2 O 3 , and the surface thereof is modified as shown in FIG. Ag-Pd layer 3a, which is a Pd alloy as a catalyst for the quality reaction, is applied by a thick film printing method or the like. The lower end of the hydrogen separation tube 3 is
It was inserted into a cylindrical metal fixing member 6 made of an e-Ni-Co alloy or the like, and the outer peripheral surface of the lower end was joined via a sealing glass 7.
【０００７】[0007]
【発明が解決しようとする課題】しかしながら、上記従
来の改質器においては、水素分離管３は軟化点が５００
〜７００℃程度の封着用ガラス７で接合固定されおり、
またその接合部はバーナ５付近の５００℃以上の高温環
境にあるため、封着用ガラス７が軟化して接合性が劣化
し易い環境にあった。また、改質器内部では動作時にメ
タノール，水蒸気，燃料ガス等の流動のため常時細かな
振動が発生しており、上記の高温環境状態で微振動が長
時間に及び水素分離管３に加えられたり、機械的衝撃が
加えられると、その接合部が破壊されて改質器が機能し
なくなるという問題があった。However, in the above-mentioned conventional reformer, the hydrogen separation tube 3 has a softening point of 500.
It is bonded and fixed with a glass 7 for sealing at about 700 ° C.,
In addition, since the joint was in a high-temperature environment of 500 ° C. or more near the burner 5, the sealing glass 7 was softened and the joining property was easily deteriorated. Further, in the reformer, fine vibrations are constantly generated due to the flow of methanol, water vapor, fuel gas, etc. during operation, and fine vibrations are applied to the hydrogen separation pipe 3 for a long time in the high temperature environment described above. Or when a mechanical impact is applied, the joint is broken and the reformer does not function.
【０００８】従って、本発明は上記事情に鑑みて完成さ
れたものであり、その目的は、水素分離管の接合性を改
善して、５００℃以上の高温環境でも接合強度が保持さ
れ、振動や衝撃によって接合部が破壊されないものとす
ることにある。Accordingly, the present invention has been completed in view of the above circumstances, and an object of the present invention is to improve the joining property of a hydrogen separation tube so that the joining strength is maintained even in a high temperature environment of 500 ° C. or more, and vibration and The object is to prevent the joint from being broken by the impact.
【０００９】[0009]
【課題を解決するための手段】本発明は、容器体として
の外囲器内に、該外囲器内を２００〜６００℃に加熱す
る燃焼器と、炭化水素系ガスを含む原料ガスが内部で流
通されるとともに水素分離管が内蔵された改質反応炉と
を具備した燃料電池用改質器において、前記水素分離管
は、表面に厚さ１０〜３０μｍのＡｇ−Ｐｄ合金層が被
着された多孔質セラミックスから成るとともに一端が開
口され他端が閉じられており、かつ前記一端側の外周面
または内周面に形成された厚さ５〜６０μｍのＡｇ−Ｃ
ｕ−Ｔｉ合金から成るメタライズ層が、７００℃以上前
記Ａｇ−Ｐｄ合金層の融点未満の融点を有するロウ材を
介して筒状の金属製固定部材の内周面または外周面に接
合されることにより、前記改質反応炉内に固定されてい
ることを特徴とする。According to the present invention, there is provided an envelope as a container, wherein a combustor for heating the interior to 200 to 600 ° C. and a raw material gas containing a hydrocarbon-based gas are contained therein. And a reformer for a fuel cell having a reforming reactor with a built-in hydrogen separation tube, wherein the hydrogen separation tube has an Ag-Pd alloy layer having a thickness of 10 to 30 μm deposited on the surface thereof. Ag-C having a thickness of 5 to 60 μm, which is formed on the outer peripheral surface or the inner peripheral surface of the one end side and is formed on the one end side and the other end is closed.
A metallized layer made of a u-Ti alloy is joined to the inner or outer peripheral surface of the cylindrical metal fixing member via a brazing material having a melting point of 700 ° C. or more and less than the melting point of the Ag—Pd alloy layer. And is fixed in the reforming reaction furnace.
【００１０】本発明は、上記の構成により、水素分離管
の接合性を改善して、５００℃以上の高温環境でも接合
強度が長期にわたり保持され、振動や衝撃によって接合
部が破壊されず、その結果改質器の機能を長期間維持で
きるものとすることにある。According to the present invention, with the above-described structure, the joining property of the hydrogen separation tube is improved, the joining strength is maintained for a long time even in a high temperature environment of 500 ° C. or more, and the joint is not broken by vibration or impact. The object is to maintain the function of the result reformer for a long time.
【００１１】また、前記メタライズ層の厚さが５μｍ〜
６０μｍであることにより、改質反応の触媒であるＡｇ
−Ｐｄ合金層とメタライズ層とが反応して、それらの成
分が相互に拡散し接合強度が劣化するのを抑制できる。The metallized layer has a thickness of 5 μm or less.
When the thickness is 60 μm, Ag which is a catalyst of the reforming reaction is used.
-It is possible to suppress the reaction between the Pd alloy layer and the metallized layer, the diffusion of these components mutually, and the deterioration of the bonding strength.
【００１２】前記ロウ材の融点が７００℃以上前記Ａｇ
−Ｐｄ合金層の融点未満であることにより、ロウ材が６
００℃程度の改質反応時の温度で軟化溶融することがな
く、またロウ付け時の温度によりＡｇ−Ｐｄ合金層が軟
化溶融することがない。従って、改質器を長期間にわた
って動作させることが可能となり、その寿命を長寿命化
し得る。The melting point of the brazing material is at least 700 ° C.
-Less than the melting point of the Pd alloy layer,
There is no softening and melting at the temperature of the reforming reaction of about 00 ° C., and no softening and melting of the Ag—Pd alloy layer due to the temperature at the time of brazing. Therefore, the reformer can be operated for a long period of time, and its life can be extended.
【００１３】さらには、前記Ａｇ−Ｐｄ合金層とＡｇ−
Ｃｕ−Ｔｉ合金から成るメタライズ層は、それらのＡｇ
が相互に拡散され、酸化物混合ソルダーを形成して強固
な接合が可能となる。Further, the Ag-Pd alloy layer and the Ag-Pd
Metallized layers made of Cu-Ti alloy are
Are diffused into each other to form an oxide mixed solder, thereby enabling a strong bonding.
【００１４】[0014]
【発明の実施の形態】本発明の改質器について以下に説
明する。図１は、本発明の改質器の断面図であり、同図
において、３は、Ｙ2Ｏ3を約８ｍｏｌ％ドープした多孔
質の安定化ジルコニア（ＹＳＺ）セラミックス等から成
り、一端が開口され他端が閉じられた筒状とされた水素
分離管、３ａは、水素分離管３の表面に形成され、改質
反応の触媒のＰｄを含むＡｇ−Ｐｄ合金層、６は、Ｆｅ
−Ｎｉ−Ｃｏ合金等の金属から成り、水素分離管３を固
定するための筒状の金属製固定部材（以下、固定部材と
いう）、８は、水素分離管３の開口された一端側の外周
面に被着されたＡｇ−Ｃｕ−Ｔｉ合金から成るメタライ
ズ層、９は接合用のロウ材である。なお、改質器全体の
基本構成は図３のものと同様であり、その詳細な説明は
省略する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The reformer of the present invention will be described below. FIG. 1 is a cross-sectional view of a reformer of the present invention. In FIG. 1, reference numeral 3 denotes a porous stabilized zirconia (YSZ) ceramic doped with about 8 mol% of Y 2 O 3 , and one end is opened. A cylindrical hydrogen separation tube 3a having the other end closed is formed on the surface of the hydrogen separation tube 3, and an Ag-Pd alloy layer containing Pd as a catalyst for the reforming reaction.
A tubular metal fixing member (hereinafter, referred to as a fixing member) made of a metal such as a Ni-Co alloy for fixing the hydrogen separation tube 3; A metallized layer 9 made of an Ag-Cu-Ti alloy adhered to the surface, and 9 is a brazing filler metal. The basic configuration of the entire reformer is the same as that of FIG. 3, and a detailed description thereof will be omitted.
【００１５】本発明において、原料ガスに含まれる炭化
水素系ガスとしては、メタノール，メタン，エタノー
ル，ＬＰＧ，ガソリン，軽油等が、容易に改質されて水
素ガスを分離できる点で好適である。また、原料ガス中
には、炭化水素系ガスの燃焼反応および改質反応等を行
うための酸素（Ｏ2），水蒸気（Ｈ2Ｏ）等が含まれる。
なお、この原料ガスは、図３に示すように、改質反応炉
の炉体２内に水素分離管３の雰囲気ガスとして供給され
炉体２内を流通し、改質反応等により水素ガスが水素分
離管３内に分離吸収される。そして、一部の未反応ガス
等を含む改質排ガスが排気口より排出される。In the present invention, as the hydrocarbon-based gas contained in the raw material gas, methanol, methane, ethanol, LPG, gasoline, light oil and the like are preferable because they can be easily reformed and hydrogen gas can be separated. The source gas contains oxygen (O 2 ), steam (H 2 O), and the like for performing a combustion reaction, a reforming reaction, and the like of the hydrocarbon-based gas.
As shown in FIG. 3, this raw material gas is supplied into the furnace body 2 of the reforming reaction furnace as an atmospheric gas of the hydrogen separation tube 3 and circulates through the furnace body 2, and hydrogen gas is generated by the reforming reaction or the like. Separated and absorbed in the hydrogen separation tube 3. Then, the reformed exhaust gas including a part of the unreacted gas and the like is discharged from the exhaust port.
【００１６】本発明の水素分離管３は、Ｙ2Ｏ3を約８ｍ
ｏｌ％ドープした多孔質の安定化ジルコニア（ＹＳＺ）
セラミックス等から成るが、これに限らず、２００〜６
００℃の高温環境でメタノール（ＣＨ3ＯＨ）等の炭化
水素系ガス，水蒸気（Ｈ2Ｏ），酸素（Ｏ2），二酸化炭
素（ＣＯ2），一酸化炭素（ＣＯ），水素ガス（Ｈ2）等
のガスに対して化学的に安定なセラミックスであればよ
い。また、多孔質の水素分離管３の気孔率は８０〜９７
％程度がよく、８０％未満では、水素ガスを効率良く水
素分離管３の内部に取り込むことが困難となり、９７％
を超えると、水素ガス以外のガスが水素分離管３の内部
に侵入し易くなる。The hydrogen separation tube 3 of the present invention has a Y 2 O 3 of about 8 m.
ol% doped porous stabilized zirconia (YSZ)
It is made of ceramics or the like, but is not limited thereto.
In a high temperature environment of 00 ° C., a hydrocarbon gas such as methanol (CH 3 OH), water vapor (H 2 O), oxygen (O 2 ), carbon dioxide (CO 2 ), carbon monoxide (CO), hydrogen gas (H 2 ) Any ceramics that are chemically stable with respect to such gases may be used. The porosity of the porous hydrogen separation tube 3 is 80-97.
%, And if it is less than 80%, it becomes difficult to efficiently take in hydrogen gas into the inside of the hydrogen separation tube 3, and 97%
When it exceeds, it becomes easy for gas other than hydrogen gas to enter the inside of the hydrogen separation tube 3.
【００１７】また、水素分離管３の表面には、改質反応
の触媒であるＰｄを含むＡｇ−Ｐｄ合金層が公知の厚膜
印刷法等により被着されており、これは電子混合導電体
として機能する。On the surface of the hydrogen separation tube 3, an Ag-Pd alloy layer containing Pd, which is a catalyst for the reforming reaction, is applied by a known thick film printing method or the like. Function as
【００１８】上記Ａｇ−Ｐｄ合金層の厚さは１０〜３０
μｍであるが、１０μｍでは、水素ガス以外のガスを透
過させることになり、３０μｍを超えると、水素ガスが
効率良く透過することができなくなる。The thickness of the Ag-Pd alloy layer is 10-30.
Although it is μm, if it is 10 μm, a gas other than hydrogen gas is permeable, and if it exceeds 30 μm, hydrogen gas cannot be efficiently transmitted.
【００１９】この水素分離管３の形状は、一端が開口さ
れ他端が閉じられた筒状であり、具体的には円筒状、ま
たは断面が三角形，四角形，六角形等の多角柱状でもよ
い。ただし、製造の容易さ、原料ガスとの接触面積の大
きさ等の点で円筒状のものが好ましい。また、水素分離
管３の断面積を可変とし、改質反応炉内の最も改質反応
が起こり易い部位でその断面積を若干大きくすることも
できる。The shape of the hydrogen separation tube 3 is a cylindrical shape having one end opened and the other end closed, and may be specifically a cylindrical shape or a polygonal column having a triangular, quadrangular or hexagonal cross section. However, a cylindrical shape is preferable in terms of ease of production, the size of the contact area with the source gas, and the like. Further, the cross-sectional area of the hydrogen separation tube 3 can be made variable, and the cross-sectional area can be slightly increased at a portion where the reforming reaction is most likely to occur in the reforming reaction furnace.
【００２０】そして、水素分離管３の一端側の外周面ま
たは内周面が、筒状の固定部材６の内周面または外周面
に接合される。この水素分離管３の内部に取り込まれた
水素ガスは、固定部材６に連結され外部に通じる排気管
等により、外部の燃料電池に供給される。The outer peripheral surface or inner peripheral surface on one end side of the hydrogen separation tube 3 is joined to the inner peripheral surface or outer peripheral surface of the cylindrical fixing member 6. The hydrogen gas taken into the hydrogen separation pipe 3 is supplied to an external fuel cell via an exhaust pipe connected to the fixing member 6 and leading to the outside.
【００２１】また、本発明において、水素分離管３の開
口を有する一端側の外周面または内周面には、酸素に対
する強い親和力を有する金属、所謂活性金属であるＴｉ
を含むＡｇ−Ｃｕ−Ｔｉ合金から成るメタライズ層８が
形成されており、活性金属のＴｉとＡｇ，Ｎｉおよび遷
移金属との合金は、高温でセラミックスの酸化物中に拡
散して緻密で強固な結合を形成する。例えば、メタライ
ズ層８はＡｇ７２ｗｔ（重量）％−Ｃｕ２８ｗｔ％共晶
合金ロウにＴｉを２〜３重量部程度加えたＡｇ−Ｃｕ−
Ｔｉ合金を含有する金属ペーストを塗布し、不活性また
は真空雰囲気中で１０００℃程度に加熱することにより
形成される。In the present invention, a metal having a strong affinity for oxygen, that is, a so-called active metal, is provided on the outer peripheral surface or the inner peripheral surface at one end of the hydrogen separation tube 3 having the opening.
A metallized layer 8 made of an Ag—Cu—Ti alloy containing is formed. The alloy of the active metal Ti and Ag, Ni, and the transition metal diffuses into the oxide of the ceramic at a high temperature and is dense and strong. Form a bond. For example, the metallized layer 8 is made of Ag-Cu- obtained by adding about 2 to 3 parts by weight of Ti to a eutectic alloy wax of 72 wt% (wt) -28 wt% of Cu.
It is formed by applying a metal paste containing a Ti alloy and heating it to about 1000 ° C. in an inert or vacuum atmosphere.
【００２２】また、上記のメタライズ層８とすること
で、ロウ材９との濡れ性が向上する。濡れ性が向上する
ことによって、金属製の固定部材６との接合強度がきわ
めて増大し、改質器の寿命を大きく伸ばすことが可能と
なる。さらには、Ｔｉを２〜３重量部程度含むことによ
りメタライズ層８の融点が約１０℃上昇し、７８０〜７
９０℃となる。その結果、５００℃以上、最高で６００
℃程度で動作する改質器において、水素分離管３の接合
部が軟化しにくくなり、安定的な運転が可能となる。The metallization layer 8 improves the wettability with the brazing material 9. By improving the wettability, the bonding strength with the metal fixing member 6 is extremely increased, and the life of the reformer can be greatly extended. Further, by containing about 2 to 3 parts by weight of Ti, the melting point of the metallized layer 8 increases by about 10 ° C.
90 ° C. As a result, 500 ° C or more, up to 600
In the reformer that operates at about ° C, the junction of the hydrogen separation tube 3 is hardly softened, and stable operation is possible.
【００２３】また、メタライズ層８の厚さは５〜６０μ
ｍであるが、５μｍ未満では、改質反応の触媒であるＡ
ｇ−Ｐｄ合金層３ａとメタライズ層８とが反応して接合
強度が劣化し易くなる。６０μｍを超えると、表面の凹
凸が大きくなり接合性が低下するため、均一で接合性の
良好なメタライズ層８を形成するうえで６０μｍ以下と
する。The thickness of the metallized layer 8 is 5 to 60 μm.
m, but when it is less than 5 μm, A, which is a catalyst for the reforming reaction,
The g-Pd alloy layer 3a reacts with the metallized layer 8 to easily deteriorate the bonding strength. If the thickness exceeds 60 μm, the surface roughness becomes large and the bonding property is reduced. Therefore, the thickness is set to 60 μm or less for forming a uniform metallized layer 8 having good bonding property.
【００２４】さらに、メタライズ層８の金属分離管３の
中心軸方向に平行な方向での長さについて、メタライズ
層８の端部（図１では上端部）は固定部材６端部（上端
部）から１〜３ｍｍ突出していることが良い。１ｍｍ未
満では、メタライズ層８の端部付近にロウ材９の溜りが
でき、ロウ材９のメニスカスの形状が理想的な山裾状と
ならないため、接合強度が著しく低下する。３ｍｍを超
えると、ロウ材９の流れが大きくなり、メタライズ層８
と固定部材６との間に隙間ができ易くなり、接合は可能
だがガス漏れを防ぐような封止が困難となる。Further, regarding the length of the metallization layer 8 in the direction parallel to the central axis direction of the metal separation tube 3, the end (the upper end in FIG. 1) of the metallization layer 8 is the end (the upper end) of the fixing member 6. It is good that it protrudes from 1 to 3 mm. When the thickness is less than 1 mm, the brazing material 9 is accumulated near the end of the metallized layer 8, and the meniscus shape of the brazing material 9 does not become an ideal mountain skirt shape, so that the joining strength is significantly reduced. If it exceeds 3 mm, the flow of the brazing material 9 increases, and the metallized layer 8
It is easy to form a gap between the metal member and the fixing member 6, and it is possible to perform joining, but it is difficult to perform sealing so as to prevent gas leakage.
【００２５】水素分離管３の一端側を固定部材６に接合
させるためのロウ材９は、改質反応時の温度により軟化
溶融しないものとし、融点が７００℃以上のＡｇ−Ｃｕ
合金等がよい。また、Ａｇ−Ｐｄ合金層３ａを軟化溶融
させないために、Ａｇ−Ｐｄ合金層３ａの融点未満のも
のとする。例えば、Ａｇ−Ｐｄ合金層３ａの融点は約８
５０℃である。The brazing material 9 for joining one end of the hydrogen separation tube 3 to the fixing member 6 is not softened and melted by the temperature during the reforming reaction, and has a melting point of Ag-Cu of 700 ° C. or more.
Alloys and the like are good. In order to prevent the Ag-Pd alloy layer 3a from softening and melting, the melting point is lower than the melting point of the Ag-Pd alloy layer 3a. For example, the melting point of the Ag-Pd alloy layer 3a is about 8
50 ° C.
【００２６】本発明の固定部材６は、熱膨張係数が１０
×１０-6〜１３×１０-6／℃と小さい金属、例えばＦｅ
−Ｎｉ−Ｃｏ合金，Ｆｅ−Ｎｉ合金等から成るのがよ
い。また固定部材６の形状は、水素分離管３と断面形状
が相似形のものがよく、円筒状、または断面が三角形
状，四角形状，六角形状等の多角柱状である。The fixing member 6 of the present invention has a coefficient of thermal expansion of 10
A metal as small as × 10 -6 to 13 × 10 -6 / ° C.
-Ni-Co alloy, Fe-Ni alloy, etc. The shape of the fixing member 6 is preferably similar to that of the hydrogen separation tube 3 in cross section. The fixing member 6 has a cylindrical shape or a polygonal column shape such as a triangular shape, a square shape, or a hexagonal shape.
【００２７】かくして、本発明は、水素分離管の接合性
を改善して、５００℃以上の高温環境でも接合強度が長
期にわたり保持され、振動や衝撃によって接合部が破壊
されず、その結果改質器の機能を長期間維持できるとい
う作用効果を有する。Thus, the present invention improves the joining property of the hydrogen separation tube, maintains the joining strength for a long time even in a high temperature environment of 500 ° C. or more, and does not destroy the joined portion due to vibration or impact. It has the effect that the function of the vessel can be maintained for a long time.
【００２８】なお、本発明は上記実施形態に限定される
ものではなく、本発明の要旨を逸脱しない範囲内におい
て種々の変更を行なうことは何等差し支えない。It should be noted that the present invention is not limited to the above embodiment, and that various changes may be made without departing from the spirit of the present invention.
【００２９】[0029]
【実施例】本発明の実施例について以下に説明する。 （実施例）図１の水素分離管３を以下のようにして接合
し構成した。Ｙ2Ｏ3を約８ｍｏｌ％ドープした、気孔率
が９７％の安定化ジルコニアセラミックスから成り、上
端が閉じ下端が開口とされた円筒状の水素分離管３の表
面に、厚さ２０μｍのＡｇ−Ｐｄ合金層を厚膜印刷法に
より形成した。この水素分離管３の下端側の外周面に、
厚さが３０μｍで、水素分離管３の中心軸方向に平行な
方向での長さに関して固定部材３の端部より１．５mm端
部が突出したＡｇ−Ｃｕ−Ｔｉ合金（Ａｇ７２ｗｔ％−
Ｃｕ２８ｗｔ％共晶合金ロウにＴｉを３重量部加えたも
の）から成るメタライズ層８を被着させた。このメタラ
イズ層８上を、厚さ５μｍのＮｉメッキ層で被覆した。Embodiments of the present invention will be described below. (Example) The hydrogen separation tube 3 of FIG. 1 was joined and configured as follows. A 20-μm-thick Ag— is formed on a surface of a cylindrical hydrogen separation tube 3 made of stabilized zirconia ceramics doped with about 8 mol% of Y 2 O 3 and having a porosity of 97% and having an upper end and an open lower end. A Pd alloy layer was formed by a thick film printing method. On the outer peripheral surface on the lower end side of the hydrogen separation tube 3,
An Ag-Cu-Ti alloy (Ag 72 wt%-
A metallized layer 8 made of Cu 28 wt% eutectic alloy braze with 3 parts by weight of Ti) was applied. The metallized layer 8 was covered with a 5 μm thick Ni plating layer.
【００３０】そして、このメタライズ層８にほぼ相当す
る部位と、Ｆｅ−Ｎｉ−Ｃｏ合金からなる円筒状の固定
部材６の内周面とを、融点が７７０℃で、２５μｍの隙
間を埋めるためにφ（断面の直径）０．３ｍｍの線状と
されたＡｇ−Ｃｕ合金から成るロウ材９により、８１０
℃に加熱して接合させた。これを本実施例の製品Ａとし
た。Then, a portion substantially corresponding to the metallized layer 8 and the inner peripheral surface of the cylindrical fixing member 6 made of an Fe—Ni—Co alloy are filled with a melting point of 770 ° C. and a gap of 25 μm. 810 is formed by a brazing material 9 made of an Ag-Cu alloy having a 0.3 mm diameter (cross-sectional diameter).
C. for bonding. This was designated as product A of the present example.
【００３１】また、比較例１として、Ａｇ−Ｃｕ−Ｔｉ
合金から成るメタライズ層８およびＮｉメッキ層がない
以外は上記実施例と同様に作製したものを製品Ｂとし
た。As Comparative Example 1, Ag—Cu—Ti
The product B was manufactured in the same manner as in the above example except that the metallized layer 8 made of an alloy and the Ni plating layer were not provided.
【００３２】比較例２として、Ａｇ−Ｃｕ−Ｔｉ合金か
ら成るメタライズ層８の代わりにＮｉメッキ層を施した
以外は上記実施例と同様に作製したものを製品Ｃとし
た。As Comparative Example 2, a product C was prepared in the same manner as in the above example except that a Ni plating layer was applied instead of the metallized layer 8 made of an Ag-Cu-Ti alloy.
【００３３】比較例３として、図２の従来技術による融
点が８００℃の封着用ガラス７により接合した以外は上
記実施例と同様に作製したものを製品Ｄとした。As Comparative Example 3, a product D was prepared in the same manner as in the above-mentioned Example except that it was joined with the sealing glass 7 having a melting point of 800 ° C. according to the prior art shown in FIG.
【００３４】これらの製品Ａ〜Ｄのそれぞれについて、
大気雰囲気中で５００℃に加熱して１０分間保持した
後、振動試験｛MIL-STD（Military standard:アメリカ
軍用規格）-202F METHOD210A｝および衝撃試験（MIL-S
TD-202F METHOD213A）を行い、その接合部に異常がな
いか確認した。その結果、製品Ａは何らの異常も確認さ
れなかった。製品Ｂは、ロウ材９による接合後に異常が
発生した。即ち、水素分離管３表面のＡｇ−Ｐｄ合金層
中のＡｇと、Ａｇ−Ｃｕ合金のロウ材９中のＡｇとが、
加熱処理により互いに混ざり合い、面積の広いＡｇ−Ｐ
ｄ合金層側にＡｇが拡散して、水素分離管３と固定部材
６との接合部に隙間が発生し接合不良となった。製品Ｃ
は、振動試験と引き続き行った衝撃試験の後に接合部に
亀裂が発生した。製品Ｄは、振動試験と衝撃試験の後に
接合部が破壊された。For each of these products A to D,
After heating to 500 ° C in air atmosphere and holding for 10 minutes, vibration test {MIL-STD (Military standard: US military standard) -202F METHOD210A} and impact test (MIL-S
TD-202F METHOD213A) was performed and it was confirmed that there was no abnormality in the joint. As a result, no abnormality was confirmed for the product A. Product B had an abnormality after joining with brazing material 9. That is, Ag in the Ag—Pd alloy layer on the surface of the hydrogen separation tube 3 and Ag in the brazing material 9 of the Ag—Cu alloy are:
Ag-P with large area mixed with each other by heat treatment
Ag diffused into the d-alloy layer side, and a gap was generated at the joint between the hydrogen separation pipe 3 and the fixing member 6, resulting in poor joining. Product C
In the test, after the vibration test and the subsequent impact test, a crack was generated in the joint. The joint of the product D was broken after the vibration test and the impact test.
【００３５】上記のように、本発明の製品Ａは各層間が
強固に接合され、５００℃程度の高温環境下においても
振動、衝撃に対して接合性が劣化することがなく、良好
な接合強度を維持できるものであることが判った。As described above, in the product A of the present invention, the layers are firmly joined to each other. Even in a high temperature environment of about 500.degree. Was maintained.
【００３６】[0036]
【発明の効果】本発明は、水素分離管は、表面に厚さ１
０〜３０μｍのＡｇ−Ｐｄ合金層が被着された多孔質セ
ラミックスから成るとともに一端が開口され他端が閉じ
られており、かつ前記一端側の外周面または内周面に形
成された厚さ５〜６０μｍのＡｇ−Ｃｕ−Ｔｉ合金から
成るメタライズ層が、７００℃以上前記Ａｇ−Ｐｄ合金
層の融点未満の融点を有するロウ材を介して筒状の金属
製固定部材の内周面または外周面に接合されることによ
り、改質反応炉内に固定されていることにより、５００
℃以上の高温環境下でも接合強度が長期にわたり保持さ
れ、振動や衝撃によって接合部が破壊されず、その結果
改質器の機能を長期間維持できるという作用効果を有す
る。According to the present invention, the hydrogen separation tube has a thickness of 1 mm on the surface.
It is made of porous ceramics having an Ag-Pd alloy layer of 0 to 30 µm, has one end opened and the other end closed, and has a thickness 5 formed on the outer peripheral surface or inner peripheral surface on the one end side. A metallized layer made of an Ag-Cu-Ti alloy having a thickness of ６０60 μm and an inner or outer peripheral surface of a cylindrical metal fixing member via a brazing material having a melting point of 700 ° C. or more and less than the melting point of the Ag-Pd alloy layer. By being fixed in the reforming reactor,
The joint strength is maintained for a long time even in a high-temperature environment of not less than ° C., and the joint is not destroyed by vibration or impact. As a result, the function of the reformer can be maintained for a long time.
【図１】本発明による水素分離管とそれが接合固定され
る固定部材の断面図である。FIG. 1 is a sectional view of a hydrogen separation tube according to the present invention and a fixing member to which the hydrogen separation tube is joined and fixed.
【図２】従来の水素分離管と固定部材の断面図である。FIG. 2 is a sectional view of a conventional hydrogen separation tube and a fixing member.
【図３】燃料電池用の改質器の断面図である。FIG. 3 is a sectional view of a reformer for a fuel cell.
【図４】水素分離管の機能を説明するためのものであ
り、改質反応炉と水素分離管の部分断面斜視図である。FIG. 4 is a partial sectional perspective view of a reforming reactor and a hydrogen separation tube for explaining the function of the hydrogen separation tube.
１：外囲器 ２：炉体 ３：水素分離管 ３ａ：Ａｇ−Ｐｄ合金層 ４：改質触媒 ５：バーナ ６：固定部材 ８：メタライズ層 ９：ロウ材 1: envelope 2: furnace body 3: hydrogen separation tube 3a: Ag-Pd alloy layer 4: reforming catalyst 5: burner 6: fixing member 8: metallization layer 9: brazing material
───────────────────────────────────────────────────── 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） Ｈ０１Ｍ 8/06 Ｈ０１Ｍ 8/06 Ｇ Ｆターム(参考） 4D006 GA41 HA21 JA22A JA22C JA30A JA30C LA06 MA02 MA06 MA24 MA31 MC02X MC03X MC90 NA45 PA01 PB18 PB66 PC80 4G040 EA02 EA03 EA06 EB33 EB46 FA02 FC01 FE01 5H027 AA02 BA01 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) H01M 8/06 H01M 8/06 GF term (Reference) 4D006 GA41 HA21 JA22A JA22C JA30A JA30C LA06 MA02 MA06 MA24 MA31 MC02X MC03X MC90 NA45 PA01 PB18 PB66 PC80 4G040 EA02 EA03 EA06 EB33 EB46 FA02 FC01 FE01 5H027 AA02 BA01
Claims (1)
２００〜６００℃に加熱する燃焼器と、炭化水素系ガス
を含む原料ガスが内部で流通されるとともに水素分離管
が内蔵された改質反応炉とを具備した燃料電池用改質器
において、前記水素分離管は、表面に厚さ１０〜３０μ
ｍのＡｇ−Ｐｄ合金層が被着された多孔質セラミックス
から成るとともに一端が開口され他端が閉じられてお
り、かつ前記一端側の外周面または内周面に形成された
厚さ５〜６０μｍのＡｇ−Ｃｕ−Ｔｉ合金から成るメタ
ライズ層が、７００℃以上前記Ａｇ−Ｐｄ合金層の融点
未満の融点を有するロウ材を介して筒状の金属製固定部
材の内周面または外周面に接合されることにより、前記
改質反応炉内に固定されていることを特徴とする燃料電
池用改質器。1. A combustor for heating an inside of an envelope as a container body to 200 to 600 ° C., a raw material gas containing a hydrocarbon-based gas being circulated therein, and a hydrogen separation tube. Wherein the hydrogen separation tube has a thickness of 10 to 30 μm on the surface thereof.
m made of a porous ceramic having an Ag-Pd alloy layer adhered thereto, having one end opened and the other end closed, and a thickness of 5 to 60 μm formed on the outer peripheral surface or the inner peripheral surface on the one end side. Is bonded to the inner or outer peripheral surface of the cylindrical metal fixing member via a brazing material having a melting point of 700 ° C. or more and less than the melting point of the Ag—Pd alloy layer. The fuel cell reformer is fixed in the reforming reaction furnace.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000093729A JP3878786B2 (en) | 2000-03-30 | 2000-03-30 | Fuel cell reformer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000093729A JP3878786B2 (en) | 2000-03-30 | 2000-03-30 | Fuel cell reformer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001278601A true JP2001278601A (en) | 2001-10-10 |
| JP3878786B2 JP3878786B2 (en) | 2007-02-07 |
Family
ID=18608874
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000093729A Expired - Fee Related JP3878786B2 (en) | 2000-03-30 | 2000-03-30 | Fuel cell reformer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3878786B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006032192A (en) * | 2004-07-20 | 2006-02-02 | Toyota Motor Corp | Fuel cell, hydrogen separation film module and manufacturing method thereof |
| JP2006273658A (en) * | 2005-03-29 | 2006-10-12 | Nippon Steel Corp | Composite structure and its forming process |
| JP2006314877A (en) * | 2005-05-11 | 2006-11-24 | Ngk Spark Plug Co Ltd | Hydrogen separator |
| JP2007253152A (en) * | 2005-07-14 | 2007-10-04 | Daikin Ind Ltd | Hydrogen separator and hydrogen manufacturing apparatus |
| JP2007254173A (en) * | 2006-03-20 | 2007-10-04 | Nippon Steel Corp | Composite structure, method for producing composite structure, film type oxygen separator, and film type reactor |
| JP2007269600A (en) * | 2006-03-31 | 2007-10-18 | Ngk Spark Plug Co Ltd | Hydrogen separation apparatus and hydrogen production system |
| JP2010036080A (en) * | 2008-08-03 | 2010-02-18 | National Institute Of Advanced Industrial & Technology | Hydrogen gas separation material with elevated temperature resistance which does not deteriorate under elevated temperature hyperbaric pressure-humid environment for a long term |
| KR101125098B1 (en) * | 2009-04-22 | 2012-03-21 | 최영종 | Sealing nethod ane metal granule using the same SOFC |
-
2000
- 2000-03-30 JP JP2000093729A patent/JP3878786B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006032192A (en) * | 2004-07-20 | 2006-02-02 | Toyota Motor Corp | Fuel cell, hydrogen separation film module and manufacturing method thereof |
| JP2006273658A (en) * | 2005-03-29 | 2006-10-12 | Nippon Steel Corp | Composite structure and its forming process |
| JP2006314877A (en) * | 2005-05-11 | 2006-11-24 | Ngk Spark Plug Co Ltd | Hydrogen separator |
| JP2007253152A (en) * | 2005-07-14 | 2007-10-04 | Daikin Ind Ltd | Hydrogen separator and hydrogen manufacturing apparatus |
| JP2007254173A (en) * | 2006-03-20 | 2007-10-04 | Nippon Steel Corp | Composite structure, method for producing composite structure, film type oxygen separator, and film type reactor |
| JP2007269600A (en) * | 2006-03-31 | 2007-10-18 | Ngk Spark Plug Co Ltd | Hydrogen separation apparatus and hydrogen production system |
| JP2010036080A (en) * | 2008-08-03 | 2010-02-18 | National Institute Of Advanced Industrial & Technology | Hydrogen gas separation material with elevated temperature resistance which does not deteriorate under elevated temperature hyperbaric pressure-humid environment for a long term |
| KR101125098B1 (en) * | 2009-04-22 | 2012-03-21 | 최영종 | Sealing nethod ane metal granule using the same SOFC |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3878786B2 (en) | 2007-02-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5204958B2 (en) | Zygote | |
| US20070295734A1 (en) | Thermal Insulating Container for a Heat Generating Unit of a Fuel Cell System | |
| JP5554747B2 (en) | Gas seal composite and apparatus comprising the gas seal composite | |
| US8182559B2 (en) | Fuel reformer housing container and fuel reforming apparatus | |
| JP2001278601A (en) | Reformer for fuel cell | |
| JP2011522353A (en) | Sealing mechanism for high temperature fuel cell stacks | |
| JP4911917B2 (en) | Hydrogen separator | |
| JP2006273658A (en) | Composite structure and its forming process | |
| US7719192B2 (en) | Metal halide lamp with intermetal interface gradient | |
| US20050132648A1 (en) | Fuel reformer housing container and fuel reforming apparatus | |
| KR101125098B1 (en) | Sealing nethod ane metal granule using the same SOFC | |
| JP4812288B2 (en) | Fuel reformer storage container and fuel reformer | |
| JP4582923B2 (en) | Ceramic heater | |
| JP5046484B2 (en) | Fuel reformer storage container and fuel reformer | |
| JP4903380B2 (en) | Fuel reformer storage container, fuel reformer, and fuel reforming system | |
| JP4889217B2 (en) | Manufacturing method of fuel reformer | |
| JP4628090B2 (en) | Fuel reformer storage container and fuel reformer | |
| JP4948759B2 (en) | Fuel reformer storage container and fuel reformer | |
| JP4493357B2 (en) | Fuel reformer storage container and fuel reformer | |
| JP4854421B2 (en) | REACTOR AND METHOD FOR PRODUCING REACTOR | |
| JP4628069B2 (en) | Fuel reformer storage container and fuel reformer | |
| JP4458889B2 (en) | Fuel reformer storage container and fuel reformer | |
| JP4903381B2 (en) | Fuel reformer | |
| JP2005213076A (en) | Vessel for containing fuel reformer, and fuel reforming apparatus | |
| JP2006182573A (en) | Fuel-reforming device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20060712 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20060718 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060919 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20061017 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20061106 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101110 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101110 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111110 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111110 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121110 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121110 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131110 Year of fee payment: 7 |
|
| LAPS | Cancellation because of no payment of annual fees |