JP2001286742A - Hydrogen separation membrane - Google Patents
Hydrogen separation membraneInfo
- Publication number
- JP2001286742A JP2001286742A JP2000107842A JP2000107842A JP2001286742A JP 2001286742 A JP2001286742 A JP 2001286742A JP 2000107842 A JP2000107842 A JP 2000107842A JP 2000107842 A JP2000107842 A JP 2000107842A JP 2001286742 A JP2001286742 A JP 2001286742A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- barrier layer
- separation membrane
- metal
- hydrogen separation
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、高純度水素ガスの
製造装置や精製装置に適用される水素分離膜に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrogen separation membrane applied to a high-purity hydrogen gas producing apparatus and a purifying apparatus.
【０００２】[0002]
【従来の技術】従来から、高純度水素ガスの製造装置等
又は燃料電池と組み合わせた発電システムには、高純度
の水素を製造するために水素分離膜が用いられている。
この従来の水素分離膜１０１は、図７に示すように、多
数の細孔１０３を有する金属補強板を複数重ね合わせて
金属多孔質支持体１０５を作製し、該金属多孔質支持体
１０５の表面に水素透過性金属箔１０７を張り合わせた
ものである。該水素分離膜１０１を用いて水素を抽出す
る場合は、水素を含有する高圧力の原料ガスを上記水素
分離膜１０１の金属多孔質支持体１０５側に接触させる
ことによって、細孔１０３から原料ガス侵入させたの
ち、更に水素透過性金属箔１０７によって水素のみを透
過させて高純度の水素を得ることができる。しかしなが
ら、上記従来の水素分離膜１０１は、長期間使用すると
水素透過性能が低下し、該水素分離膜１０１が用いられ
る発電システム等に要求される水素透過性能を満足しな
いことがあった。2. Description of the Related Art Conventionally, a hydrogen separation membrane has been used for producing high-purity hydrogen in a high-purity hydrogen gas producing apparatus or a power generation system combined with a fuel cell.
As shown in FIG. 7, this conventional hydrogen separation membrane 101 forms a metal porous support 105 by laminating a plurality of metal reinforcing plates having a large number of pores 103, and forms a surface of the metal porous support 105. And a hydrogen-permeable metal foil 107 attached to the substrate. When hydrogen is extracted using the hydrogen separation membrane 101, a high-pressure raw material gas containing hydrogen is brought into contact with the metal porous support 105 side of the hydrogen separation membrane 101, so that the raw material gas passes through the pores 103. After the penetration, only hydrogen is permeated by the hydrogen-permeable metal foil 107 to obtain high-purity hydrogen. However, when the conventional hydrogen separation membrane 101 is used for a long period of time, the hydrogen permeation performance decreases, and the hydrogen permeation performance required for a power generation system or the like using the hydrogen separation membrane 101 may not be satisfied.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、上記課題を
解決し、長期間の間使用しても、水素透過性能が低下し
にくい水素分離膜を提供することを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to provide a hydrogen separation membrane in which hydrogen permeation performance does not easily deteriorate even when used for a long period of time.
【０００４】[0004]
【課題を解決するための手段】本発明に係る水素分離膜
は、上記目的を達成するため、複数の流通孔を有する金
属多孔質支持体と水素透過性金属箔との間にバリヤ層を
設けた水素分離膜であって、上記バリヤ層として、融点
が１８００℃以上である高融点金属を用いている。上記
バリヤ層がない場合は、金属多孔質支持体と水素透過性
金属箔が接触するため、水素透過性金属箔に含有されて
いる金属成分、例えばＰｄ等が金属多孔質支持体中に拡
散してしまい、水素透過性金属箔の水素透過性能が低下
するおそれがある。しかし、上記バリヤ層を金属多孔質
支持体と水素透過性金属箔との間に介在させることによ
って、水素透過性金属箔に含有されている金属成分が直
接に金属多孔質支持体中に拡散することがなくなり、水
素透過性能の劣化を防止することができる。さらに、バ
リヤ層として用いる金属については、１８００℃以上の
融点が必要であるが、２２００〜３４００℃が更に好ま
しい。In order to achieve the above object, a hydrogen separation membrane according to the present invention has a barrier layer provided between a metal porous support having a plurality of flow holes and a hydrogen permeable metal foil. And a high-melting point metal having a melting point of 1800 ° C. or more is used as the barrier layer. If the barrier layer is not provided, the metal porous support comes into contact with the hydrogen-permeable metal foil, so that the metal component, for example, Pd, contained in the hydrogen-permeable metal foil diffuses into the metal porous support. As a result, the hydrogen permeable performance of the hydrogen permeable metal foil may be reduced. However, by interposing the barrier layer between the metal porous support and the hydrogen-permeable metal foil, the metal component contained in the hydrogen-permeable metal foil is directly diffused into the metal porous support. And the deterioration of hydrogen permeation performance can be prevented. Further, the metal used as the barrier layer needs to have a melting point of 1800 ° C. or higher, but more preferably 2200 to 3400 ° C.
【０００５】また、本発明に係る水素分離膜の一態様で
は、上記バリヤ層として、Ｔｉ，Ｓｉ，Ａｌ，Ｍｇ，Ｃ
ａ，Ｙ，Ｚｒ，Ｈｆの群から選択される１種以上の元素
とＮ，Ｃ，Ｏ，Ｂの群から選択される１種以上の元素と
からなり、かつ、気孔率が２０％以下であるセラミック
スを用いている。上記バリヤ層は、高融点金属以外にも
セラミックスを好適に用いることができる。また、上記
気孔率は、低ければ低いほど望ましく、２０％以下、即
ち、０〜２０％とする。なお、別の態様として、０％を
超えて２０％以下とすることも可能である。さらに、本
発明に係る水素分離膜の別の態様では、上記バリヤ層を
単層又は複層に形成している。このバリヤ層を真空蒸
着、イオンフ゜レーティンク゛、ＣＶＤ等の方法で形成する場合、そ
の結晶粒界が欠陥となるおそれがあり、また、結晶は膜
成長方向に成長するので結晶粒界も膜の成長方向につな
がる。そして、上記欠陥の存在場所は材質及び膜形成条
件によって決まる結晶の大きさに依存する。従って、同
種の膜を連続して積層させる場合に、欠陥が連続する可
能性が高いのに対し、異種の膜を積層する場合は、結晶
の大きさが異なるので、欠陥即ち結晶粒界の形成場所が
不連続となる可能性が大きくなる。このため、バリヤ層
を多層構造とすることによって連続欠陥が減少し、バリ
ヤ層による拡散防止効果が増し、単層以上に水素透過性
能の劣化を抑制することができる。In one embodiment of the hydrogen separation membrane according to the present invention, the barrier layer is made of Ti, Si, Al, Mg, C
a, Y, Zr, Hf, and at least one element selected from the group consisting of N, C, O, and B, and having a porosity of 20% or less. A certain ceramic is used. Ceramics can be suitably used for the barrier layer in addition to the high melting point metal. The porosity is desirably as low as possible, and is preferably 20% or less, that is, 0 to 20%. Note that, as another aspect, it is possible to exceed 0% and set to 20% or less. Further, in another aspect of the hydrogen separation membrane according to the present invention, the barrier layer is formed as a single layer or a multilayer. When this barrier layer is formed by a method such as vacuum deposition, ion plating, CVD, or the like, the crystal grain boundaries may become defects, and since the crystals grow in the film growth direction, the crystal grain boundaries also grow. Lead to the direction. The location of the defect depends on the crystal size determined by the material and film forming conditions. Therefore, when the same kind of film is continuously stacked, the possibility that defects are continuous is high. On the other hand, when different kinds of films are stacked, the size of the crystal is different. The possibility of discontinuous locations increases. Therefore, by forming the barrier layer into a multilayer structure, continuous defects are reduced, the effect of preventing the diffusion by the barrier layer is increased, and the deterioration of hydrogen permeation performance can be suppressed more than a single layer.
【０００６】そして、本発明に係る水素分離膜の更に別
の態様では、上記金属多孔質支持体とバリヤ層との間、
又は上記水素透過性金属箔とバリヤ層との間に、Ａｇ，
Ａｕ，Ｐｔ，Ａｌ，Ｐｄ，Ｎｉの群から選択される１種
以上の元素からなる金属層を更に設けている。上記金属
層を形成することによって、バリヤ層と金属多孔質支持
体、又はバリヤ層と水素透過性金属箔との接合強度が大
幅に向上し、高圧下においてもリークなどが発生するお
それがなくなる。また、本発明に係る水素分離膜の更に
別の態様では、上記金属層を、単層又は複数層に形成し
ている。なお、本発明に係る水素分離膜の更に別の態様
では、上記金属層の厚さを０．０５〜１μｍに形成して
いる。さらに、本発明に係る水素分離膜の更に別の態様
では、上記金属層を、上記金属多孔質支持体とバリヤ層
との間、及び上記水素透過性金属箔とバリヤ層との間の
双方に設けている。[0006] In still another embodiment of the hydrogen separation membrane according to the present invention, the hydrogen separation membrane is provided between the metal porous support and the barrier layer.
Or, between the hydrogen permeable metal foil and the barrier layer, Ag,
A metal layer made of at least one element selected from the group consisting of Au, Pt, Al, Pd, and Ni is further provided. By forming the metal layer, the bonding strength between the barrier layer and the metal porous support, or between the barrier layer and the hydrogen-permeable metal foil, is greatly improved, and there is no possibility that a leak or the like occurs even under high pressure. In still another aspect of the hydrogen separation membrane according to the present invention, the metal layer is formed as a single layer or a plurality of layers. Note that, in still another embodiment of the hydrogen separation membrane according to the present invention, the thickness of the metal layer is formed to be 0.05 to 1 μm. Furthermore, in still another aspect of the hydrogen separation membrane according to the present invention, the metal layer is provided between the metal porous support and the barrier layer and between the hydrogen permeable metal foil and the barrier layer. Provided.
【０００７】[0007]
【発明の実施の形態】以下に、本発明の実施の形態につ
いて、図面を用いて詳細に説明する。図１は本発明の実
施形態に係る水素分離膜の一部を切断した斜視図、図２
は図１のＡ−Ａ線による断面図である。この水素分離膜
１は、多数の細孔３が厚さ方向に貫通して設けられた金
属多孔質支持体５と、該金属多孔質支持体５の表面側に
設けられたバリヤ層７と、該バリヤ層７の表面側に設け
られた水素透過性金属箔９とから構成されている。ま
た、バリヤ層７は、図２のように単層のものに限定され
ず、図３に示すように２層あるいは３層以上に形成して
も良い。Embodiments of the present invention will be described below in detail with reference to the drawings. FIG. 1 is a perspective view of a part of a hydrogen separation membrane according to an embodiment of the present invention, and FIG.
FIG. 2 is a sectional view taken along line AA in FIG. 1. The hydrogen separation membrane 1 includes a metal porous support 5 provided with a large number of pores 3 penetrating in the thickness direction, a barrier layer 7 provided on the surface side of the metal porous support 5, And a hydrogen-permeable metal foil 9 provided on the surface side of the barrier layer 7. Further, the barrier layer 7 is not limited to a single layer as shown in FIG. 2, but may be formed as two layers or three or more layers as shown in FIG.
【０００８】上記金属多孔質支持体５は、材質が普通鋼
やステンレス鋼等のＦｅ合金、純Ｎｉ、Ｎｉ合金、純Ｔ
ｉ、Ｔｉ合金、Ｃｒ合金などであり、その形状は、金
網、不織布、板状体又はパイプに機械加工、打ち抜き又
はエッチングなどによって細孔３を穿設したものなど種
々の態様のものを用いることができる。上記バリヤ層７
は、金属多孔質支持体５と水素透過性金属箔９との間に
配設され、多数の流通孔１１が厚さ方向に沿って設けら
れており、気孔率が小さい高融点金属又はセラミックス
で形成されている。この高融点金属は、融点が１８００
℃以上の金属であり、例えばＺｒ，Ｍｏ，Ｔａ，Ｗ，Ｃ
ｒ，Ｈｆ，Ｎｂ及びＲｕなどが挙げられる。また、上記
セラミックスは、Ｔｉ，Ｓｉ，Ａｌ，Ｍｇ，Ｃａ，Ｙ，
Ｚｒ，Ｈｆの群から選択される１種以上の元素とＮ，
Ｃ，Ｏ，Ｂの群から選択される１種以上の元素とからな
る化合物であり、例えばＴｉＮ，ＴｉＣ，ＴｉＯ2 ，Ｔ
ｉＢ，Ｓｉ3Ｎ4，ＳｉＣ，ＳｉＯ2，ＡｌＮ，Ａｌ
2Ｏ3，ＭｇＯ，ＣａＯ2，ＡｌＳｉＯx，Ｙ2Ｏ3，ＺｒＯ
2，ＴｉＡｌＮ，ＭｇＯ・Ａｌ2Ｏ3，２ＭｇＯ・ＳｉＯ2
などが挙げられる。また、バリヤ層７の厚さは０．５〜
２０μｍが好ましい。The metal porous support 5 is made of Fe alloy such as ordinary steel or stainless steel, pure Ni, Ni alloy, pure T
i, Ti alloy, Cr alloy, etc., in the form of a wire mesh, a nonwoven fabric, a plate-like body or a pipe in which various holes 3 are formed by machining, punching, etching or the like. Can be. The barrier layer 7
Is disposed between the metal porous support 5 and the hydrogen-permeable metal foil 9, has a large number of flow holes 11 along the thickness direction, and is made of a high melting point metal or ceramic having a small porosity. Is formed. This refractory metal has a melting point of 1800
And metals such as Zr, Mo, Ta, W, C
r, Hf, Nb and Ru. The ceramics described above are Ti, Si, Al, Mg, Ca, Y,
One or more elements selected from the group consisting of Zr and Hf and N,
A compound comprising at least one element selected from the group consisting of C, O, and B, for example, TiN, TiC, TiO 2 , T
iB, Si 3 N 4 , SiC, SiO 2 , AlN, Al
2 O 3 , MgO, CaO 2 , AlSiO x , Y 2 O 3 , ZrO
2 , TiAlN, MgO.Al 2 O 3 , 2MgO.SiO 2
And the like. Further, the thickness of the barrier layer 7 is 0.5 to
20 μm is preferred.
【０００９】さらに、上記水素透過性金属箔９は、Ｐｄ
箔、Ｐｄを含有する合金からなる箔、５族元素（Ｖ，Ｎ
ｂ，Ｔａ）の箔、該５族元素を含有する合金からなる箔
が好適である。この水素透過性金属箔９の好ましい例と
しては、Ｐｄ合金、ＰｄとＡｇからなる合金、Ｙ及び希
土類元素からなる群から選ばれる１種以上の金属とＰｄ
とからなる合金、５族元素単体、２種以上の５族元素の
合金、５族元素とＮｉ，Ｃｏ，Ｐｄ，Ｃｕ等の８族元素
の合金、５族元素とＴｉ，Ｍｏ，Ａｇ，Ａｕ，Ｃｕの合
金金属の単層あるいは積層膜などが挙げられる。また、
水素透過性金属箔９の厚さは０．５〜２０μｍである。Further, the hydrogen-permeable metal foil 9 is made of Pd
Foil, foil made of an alloy containing Pd, Group V element (V, N
b, Ta) foil, and a foil made of an alloy containing the Group 5 element are preferable. Preferred examples of the hydrogen-permeable metal foil 9 include a Pd alloy, an alloy composed of Pd and Ag, one or more metals selected from the group consisting of Y and rare earth elements, and Pd.
, An alloy of a group 5 element alone, an alloy of two or more group 5 elements, an alloy of a group 5 element and an element of a group 8 element such as Ni, Co, Pd, Cu, etc., a group 5 element and Ti, Mo, Ag, Au , Cu alloy metal single layer or laminated film. Also,
The thickness of the hydrogen-permeable metal foil 9 is 0.5 to 20 μm.
【００１０】上記水素分離膜１を用いて水素分離膜部材
を作製する方法を説明する。平板型の形状を有する水素
分離膜部材を作製する場合には、通気用の溝又は孔の開
いたベース板に上記水素分離膜１を重ね合わせて、ろう
付け、拡散接合、シール溶接等により外周部を接合す
る。また、管型のものを作製する場合には、通気用孔が
開いた管状のベースパイプの外周に水素分離膜１を巻き
付け、その外周部にシール溶接を施す。A method of manufacturing a hydrogen separation membrane member using the hydrogen separation membrane 1 will be described. When manufacturing a hydrogen separation membrane member having a flat plate shape, the hydrogen separation membrane 1 is superimposed on a base plate having a groove or hole for ventilation, and the outer periphery is formed by brazing, diffusion bonding, seal welding, or the like. Join the parts. In the case of manufacturing a tubular type, the hydrogen separation membrane 1 is wound around the outer periphery of a tubular base pipe having a vent hole, and seal welding is performed on the outer periphery.
【００１１】図４と図５は、上記水素透過性金属箔９と
金属多孔質支持体５との間に、バリヤ層７に加えて、更
に金属層１３を設けた水素分離膜２１を示す断面図であ
る。この金属層１３は、図４のように水素透過性金属箔
９とバリヤ層７との間、又は、図５のように金属多孔質
支持体５とバリヤ層７との間に形成する。また、これら
の図に示すように単層であっても良いが、異なる材質の
層を複数形成しても良く、さらに、水素透過性金属箔９
とバリヤ層７との間、及び、金属多孔質支持体５とバリ
ヤ層７との間の双方に配設しても良い。金属層１３の材
質は、Ａｇ，Ａｕ，Ｐｔ，Ａｌ，Ｐｄ，Ｎｉの群から選
択される１種以上の元素から構成する。この金属層１３
によって、上記バリヤ層７と水素透過性金属箔９の接合
強度、又はバリヤ層７と金属多孔質支持体５の接合強度
を高めることができ、差圧が大きい環境下における使用
に際しても、リーク等が発生するおそれがなくなる。FIGS. 4 and 5 are sectional views showing a hydrogen separation membrane 21 provided with a metal layer 13 in addition to the barrier layer 7 between the hydrogen permeable metal foil 9 and the metal porous support 5. FIG. The metal layer 13 is formed between the hydrogen-permeable metal foil 9 and the barrier layer 7 as shown in FIG. 4 or between the metal porous support 5 and the barrier layer 7 as shown in FIG. Further, as shown in these figures, a single layer may be used, but a plurality of layers of different materials may be formed.
And the barrier layer 7, and between the metal porous support 5 and the barrier layer 7. The material of the metal layer 13 is made of one or more elements selected from the group consisting of Ag, Au, Pt, Al, Pd, and Ni. This metal layer 13
Thereby, the bonding strength between the barrier layer 7 and the hydrogen-permeable metal foil 9 or the bonding strength between the barrier layer 7 and the metal porous support 5 can be increased. This eliminates the risk of occurrence.
【００１２】[0012]
【実施例】以下、実施例により本発明をさらに具体的に
説明する。 ［実施例１］水素透過性金属箔９と金属多孔質支持体５
との間にバリヤ層７を設けた水素分離膜１を形成し、図
６に示す管状のベースパイプ２３に巻き付けて管状の水
素分離膜部材２５を作製した。この水素分離膜部材２５
に水素を含んだ混合ガスを５５０℃の温度下において３
０００時間流し続けた後に水素透過量を測定し、混合ガ
スを流す前の水素透過量と比較して相対評価をした。こ
の結果を表１と表２に示すが、判定において、３０００
時間経過後の水素透過量の相対値が９０以上の場合は
○、６０〜８９の場合は△、５９以下の場合は×とし
た。ここで、紙面のスペースの関係上、実施例１の結果
を形式的に表１と表２に分けたが、表２は表１に続くも
のである。また、上記水素透過性金属箔９、バリヤ層７
及び金属多孔質支持体５の材質や、バリヤ層７の形成方
法、気孔率（欠陥密度）及び厚みも、合わせて以下の表
１と表２に示す。なお、参考のため、表１と表２の元素
の融点を以下に示す。Ｚｒが１８５２℃、Ｍｏが２６１
７℃、Ｔａが２９９８℃、Ｗが３３８０℃、Ｃｒが１８
７５℃、Ｎｉが１４５３℃、Ｆｅが１５３６℃、Ｔｉが
１６７０℃、Ａｌが６６０℃である。The present invention will be described more specifically with reference to the following examples. [Example 1] Hydrogen-permeable metal foil 9 and metal porous support 5
Then, the hydrogen separation membrane 1 provided with the barrier layer 7 was formed and wound around a tubular base pipe 23 shown in FIG. 6 to produce a tubular hydrogen separation membrane member 25. This hydrogen separation membrane member 25
A mixed gas containing hydrogen at a temperature of 550 ° C.
After flowing for 000 hours, the amount of hydrogen permeation was measured and compared with the amount of hydrogen permeation before flowing the mixed gas to make a relative evaluation. Tables 1 and 2 show the results.
When the relative value of the hydrogen permeation amount after the passage of time was 90 or more, the result was evaluated as ○; Here, the results of Example 1 were formally divided into Tables 1 and 2 due to the space on the paper, and Table 2 follows Table 1. The hydrogen permeable metal foil 9 and the barrier layer 7
Table 1 and Table 2 below also show the material of the metal porous support 5, the method of forming the barrier layer 7, the porosity (defect density), and the thickness. The melting points of the elements shown in Tables 1 and 2 are shown below for reference. Zr is 1852 ° C, Mo is 261
7 ° C, Ta 2998 ° C, W 3380 ° C, Cr 18
75 ° C., Ni is 1453 ° C., Fe is 1536 ° C., Ti is 1670 ° C., and Al is 660 ° C.
【００１３】[0013]
【表１】 [Table 1]
【００１４】[0014]
【表２】 [Table 2]
【００１５】これらの表１と表２から判るように、水素
透過性金属箔９と金属多孔質支持体５との間にバリヤ層
７を設けることによって、水素透過性能の低下を大幅に
抑制することができた。ただし、比較材１−２〜１−４
の結果をみると、バリヤ層７を設けても、該バリヤ層７
の気孔率が低い場合は水素透過性能の低下が大きいこと
が判る。さらに、本発明材１−４３〜１−５０の結果か
ら、上記バリヤ層７は、単層よりも複層の方が水素透過
性能の低下を効果的に防止することができることが判明
した。As can be seen from Tables 1 and 2, the provision of the barrier layer 7 between the hydrogen-permeable metal foil 9 and the porous metal support 5 greatly suppresses the reduction in hydrogen permeability. I was able to. However, comparative materials 1-2 to 1-4
According to the result, even if the barrier layer 7 is provided, the barrier layer 7
It can be seen that when the porosity is low, the hydrogen permeability is significantly reduced. Further, from the results of the present invention materials 1-43 to 1-50, it was found that the barrier layer 7 can more effectively prevent the hydrogen permeation performance from being lowered than the single layer.
【００１６】［実施例２］次いで、水素分離膜部材を、
温度９００℃、加圧力１ｋｇｆ／ｃｍ2 でプレスして接
合し、接合強度を評価した。接合強度が０．１ｋｇｆ／
ｃｍ2 以下では、差圧の大きな環境における使用中にリ
ークが発生するおそれがあるため、接合強度が０．１ｋ
ｇｆ／ｃｍ2 以上のものを判定において合格（○）とし
た。その結果を表３に示す。[Example 2] Next, the hydrogen separation membrane member was
Pressing was performed at a temperature of 900 ° C. under a pressure of 1 kgf / cm 2 to perform bonding, and the bonding strength was evaluated. The joint strength is 0.1kgf /
cm 2 or less, there is a possibility that a leak may occur during use in an environment with a large differential pressure, so that the bonding strength is 0.1 k
Those having gf / cm 2 or more were judged as acceptable (○) in the judgment. Table 3 shows the results.
【００１７】[0017]
【表３】 [Table 3]
【００１８】表３の比較材２−２に示すように、バリヤ
層７のみを設けた場合、５０回で破損したが、水素透過
性金属箔９とバリヤ層７との間、バリヤ層７と金属多孔
質支持体５の間、又はその両方に金属層１３を設けるこ
とにより、発停に対する耐久性が向上した。また、比較
材２−４に示すように、金属層１３を設けても、その厚
さが０．０２μｍと薄い場合は接合強度が低くなること
が判明した。なお、比較材１−１はバリヤ層７がないた
め、比較の対象ではないが、参考値として掲載した。As shown in the comparative material 2-2 in Table 3, when only the barrier layer 7 was provided, it was broken 50 times, but between the hydrogen-permeable metal foil 9 and the barrier layer 7, By providing the metal layer 13 between the metal porous supports 5 or both, the durability against start and stop was improved. Also, as shown in Comparative Material 2-4, it was found that even when the metal layer 13 was provided, when the thickness was as small as 0.02 μm, the bonding strength was low. In addition, since the comparative material 1-1 does not have the barrier layer 7, it is not a comparison target, but is shown as a reference value.
【００１９】[0019]
【発明の効果】本発明によれば、欠陥の少ない高融点金
属又はセラミックスから構成されたバリヤ層を設けたた
め、水素透過性金属箔に含有されている金属成分が直接
に金属多孔質支持に拡散することがなくなり、水素透過
性能の劣化を抑制することができる。According to the present invention, since a barrier layer composed of a high-melting point metal or a ceramic having few defects is provided, the metal component contained in the hydrogen-permeable metal foil is directly diffused into the metal porous support. And the deterioration of hydrogen permeation performance can be suppressed.
【図１】本発明に係る水素分離膜の一部を切断した斜視
図である。FIG. 1 is a perspective view in which a part of a hydrogen separation membrane according to the present invention is cut.
【図２】図１のＡ−Ａ線による断面図である。FIG. 2 is a sectional view taken along line AA of FIG.
【図３】図２のバリヤ層を２層に形成した水素分離膜を
示す断面図である。FIG. 3 is a sectional view showing a hydrogen separation membrane in which the barrier layer of FIG. 2 is formed in two layers.
【図４】図２のバリヤ層と水素透過性金属膜との間に金
属層を形成した水素分離膜を示す断面図である。FIG. 4 is a cross-sectional view illustrating a hydrogen separation membrane in which a metal layer is formed between the barrier layer and the hydrogen-permeable metal film in FIG.
【図５】図２のバリヤ層と金属多孔質支持体との間に金
属層を形成した水素分離膜を示す断面図である。FIG. 5 is a cross-sectional view showing a hydrogen separation membrane in which a metal layer is formed between the barrier layer and the metal porous support of FIG.
【図６】ベースパイプの外周に水素分離膜を張り付けた
水素分離膜部材を示す斜視図である。FIG. 6 is a perspective view showing a hydrogen separation membrane member in which a hydrogen separation membrane is attached to the outer periphery of a base pipe.
【図７】従来の水素分離膜の一部を切断した斜視図であ
る。FIG. 7 is a perspective view in which a part of a conventional hydrogen separation membrane is cut.
１，２１ 水素分離膜 ３ 細孔 ５ 金属多孔質支持体 ７ バリヤ層 ９ 水素透過性金属箔 １１ 流通孔 １３ 金属層 ２３ ベースパイプ ２５ 水素分離膜部材 1, 21 hydrogen separation membrane 3 pore 5 metal porous support 7 barrier layer 9 hydrogen permeable metal foil 11 flow hole 13 metal layer 23 base pipe 25 hydrogen separation membrane member
───────────────────────────────────────────────────── フロントページの続き (72)発明者 中野 要治 広島県広島市西区観音新町四丁目６番22号 三菱重工業株式会社広島研究所内 (72)発明者 小林 一登 東京都千代田区丸の内二丁目５番１号 三 菱重工業株式会社内 Ｆターム(参考） 4D006 GA41 HA28 KE16Q MA02 MA03 MA06 MA08 MA24 MA31 MB16 MC01X MC02X MC03X MC87 NA31 NA45 NA50 PA01 PB20 PB66 PC80 4G040 FA02 FB09 FC01 FD07 FE01 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yoji Nakano 4-6-22 Kannon Shinmachi, Nishi-ku, Hiroshima-shi, Hiroshima Mitsubishi Heavy Industries, Ltd. Hiroshima Research Laboratory (72) Inventor Kazuto Kobayashi 2-chome Marunouchi, Chiyoda-ku, Tokyo No. 5-1 F-term in Mitsubishi Heavy Industries, Ltd. (Reference) 4D006 GA41 HA28 KE16Q MA02 MA03 MA06 MA08 MA24 MA31 MB16 MC01X MC02X MC03X MC87 NA31 NA45 NA50 PA01 PB20 PB66 PC80 4G040 FA02 FB09 FC01 FD07 FE01
Claims (7)
水素を透過させるための水素透過性金属箔との間にバリ
ヤ層を設けた水素分離膜であって、上記バリヤ層とし
て、融点が１８００℃以上の高融点金属を用いたことを
特徴とする水素分離膜。1. A hydrogen separation membrane comprising a barrier layer provided between a metal porous support having a plurality of pores and a hydrogen-permeable metal foil for allowing hydrogen to pass therethrough, wherein the barrier layer has a melting point Using a high melting point metal of 1800 ° C. or higher.
ｌ，Ｍｇ，Ｃａ，Ｙ，Ｚｒ，Ｈｆの群から選択される１
種以上の元素とＮ，Ｃ，Ｏ，Ｂの群から選択される１種
以上の元素とからなり、かつ、気孔率が２０％以下であ
るセラミックスを用いたことを特徴とする水素分離膜。2. The method according to claim 1, wherein the barrier layer is Ti, Si, A.
1 selected from the group consisting of 1, Mg, Ca, Y, Zr, and Hf
A hydrogen separation membrane comprising a ceramic comprising at least one element and at least one element selected from the group consisting of N, C, O, and B and having a porosity of 20% or less.
ことを特徴とする請求項１又は２に記載の水素分離膜。3. The hydrogen separation membrane according to claim 1, wherein the barrier layer is formed as a single layer or a plurality of layers.
間、又は上記水素透過性金属箔とバリヤ層との間に、Ａ
ｇ，Ａｕ，Ｐｔ，Ａｌ，Ｐｄ，Ｎｉの群から選択される
１種以上の元素からなる金属層を更に設けたことを特徴
とする請求項１〜３のいずれかに記載の水素分離膜。4. The method according to claim 1, wherein said metal porous support and said barrier layer, or said hydrogen permeable metal foil and said barrier layer,
The hydrogen separation membrane according to any one of claims 1 to 3, further comprising a metal layer made of at least one element selected from the group consisting of g, Au, Pt, Al, Pd, and Ni.
たことを特徴とする請求項４に記載の水素分離膜。5. The hydrogen separation membrane according to claim 4, wherein the metal layer is formed as a single layer or a plurality of layers.
形成したことを特徴とする請求項４又は５に記載の水素
分離膜。6. The hydrogen separation membrane according to claim 4, wherein said metal layer has a thickness of 0.05 to 1 μm.
バリヤ層との間、及び上記水素透過性金属箔とバリヤ層
との間の双方に設けたことを特徴とする請求項４〜６の
いずれかに記載の水素分離膜。7. The method according to claim 4, wherein said metal layer is provided both between said metal porous support and said barrier layer, and between said hydrogen permeable metal foil and said barrier layer. 7. The hydrogen separation membrane according to any one of 6.
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| JP2013139382A (en) * | 2011-12-30 | 2013-07-18 | Industrial Technology Research Inst | Method for modifying porous substrate, and modified porous substrate |
| TWI449808B (en) * | 2011-12-30 | 2014-08-21 | Ind Tech Res Inst | Method for modifying porous substrate and modified porous substrate |
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