JP2002336664A - Hydrogen-permeable membrane unit and its manufacturing method - Google Patents
Hydrogen-permeable membrane unit and its manufacturing methodInfo
- Publication number
- JP2002336664A JP2002336664A JP2001143409A JP2001143409A JP2002336664A JP 2002336664 A JP2002336664 A JP 2002336664A JP 2001143409 A JP2001143409 A JP 2001143409A JP 2001143409 A JP2001143409 A JP 2001143409A JP 2002336664 A JP2002336664 A JP 2002336664A
- Authority
- JP
- Japan
- Prior art keywords
- permeable membrane
- hydrogen
- porous support
- hydrogen permeable
- alloy
- Prior art date
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Classifications
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- 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
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Fuel Cell (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、水素透過膜ユニッ
ト及びその製造方法に関するものである。The present invention relates to a hydrogen permeable membrane unit and a method for manufacturing the same.
【０００２】[0002]
【従来の技術及びその課題】従来の水素透過膜ユニット
として、例えば特開平４−３４６８２４公報に記載され
るものが知られている。これは、金網を焼結した多孔質
支持体を担体とし、この上に水素を選択的に透過させる
Ｐｄ又はＰｄ合金からなる水素透過膜を形成している。2. Description of the Related Art As a conventional hydrogen permeable membrane unit, for example, one described in Japanese Patent Application Laid-Open No. 4-346824 is known. In this method, a porous support obtained by sintering a wire mesh is used as a carrier, and a hydrogen permeable membrane made of Pd or a Pd alloy for selectively permeating hydrogen is formed thereon.
【０００３】図１１には、この種の水素透過膜を備える
水素透過膜ユニットを示す。この水素透過膜ユニット５
０は、金属製の枠体５２を備え、水素透過膜５１を枠体
５２及び多孔質支持体５３の内の少なくとも一方に、接
合部５４によつて接合させている。接合部５４は、例え
ばメッキ、ＣＶＤ（気相化学反応）、スパッタリングの
方法によつて、水素透過膜５１を枠体５２又は多孔質支
持体５３の表面に形成することで、同時に形成させてい
る。FIG. 11 shows a hydrogen permeable membrane unit having this kind of hydrogen permeable membrane. This hydrogen permeable membrane unit 5
Numeral 0 includes a metal frame 52, and the hydrogen permeable membrane 51 is bonded to at least one of the frame 52 and the porous support 53 by a bonding portion 54. The bonding portion 54 is formed simultaneously by forming the hydrogen-permeable film 51 on the surface of the frame 52 or the porous support 53 by, for example, plating, CVD (gas phase chemical reaction), or sputtering. .
【０００４】多孔質支持体５３は、セラミックス、ガラ
ス、ステンレス等の粉末や繊維の焼結体であり、水素を
通過させる連通孔を有している。この枠体５２と多孔質
支持体５３とは、リークを生じないように溶接、ろう付
けなどによつて接合され、接合部５５を有している。The porous support 53 is a sintered body of powder or fiber of ceramics, glass, stainless steel or the like, and has a communication hole through which hydrogen passes. The frame 52 and the porous support 53 are joined by welding, brazing, or the like so as not to cause a leak, and have a joint 55.
【０００５】このような水素透過膜ユニット５０は、燃
料電池の水素源として天然ガスや都市ガスを使用する
際、メンブレンリアクタ方式の水素改質器への適用が検
討されている。触媒上で天然ガス又は都市ガスと水蒸気
とが反応することにより、Ｈ2、ＣＯ、ＣＯ2 などの混
合ガスが生成し、水素透過膜５１の例えば図上で上方の
供給側に到達する。水素透過膜５１は、Ｈ2 のみを透過
させるから、供給側の混合ガス中からＨ2 のみを選択的
に分離させることができる。水素透過膜５１を矢印Ａ方
向に透過したＨ2 は、連通孔を有する多孔質支持体５３
を透過し、水素放出側に至り、水素利用装置である燃料
電池等に供給される。なお、水素透過膜５１の図上で下
方を供給側とし、Ｈ2 を矢印Ａ方向と反対方向に透過さ
せることもできる。[0005] Application of such a hydrogen permeable membrane unit 50 to a membrane reactor type hydrogen reformer when using natural gas or city gas as a hydrogen source for a fuel cell is being studied. When natural gas or city gas reacts with water vapor on the catalyst, a mixed gas such as H 2 , CO, or CO 2 is generated, and reaches a supply side of the hydrogen permeable membrane 51, for example, an upper side in the drawing. Since the hydrogen permeable membrane 51 allows only H 2 to permeate, it can selectively separate only H 2 from the mixed gas on the supply side. H 2 that has passed through the hydrogen permeable membrane 51 in the direction of arrow A is converted into a porous support 53 having communication holes.
, Reaches the hydrogen release side, and is supplied to a fuel cell or the like which is a hydrogen utilization device. The lower side of the hydrogen permeable membrane 51 in the drawing may be the supply side, and H 2 may be transmitted in the direction opposite to the arrow A direction.
【０００６】水素透過膜５１におけるＨ2 の透過は、拡
散現象を利用するので、透過方向の厚さが薄いほど、ま
た、所定の高温状態であるほど、透過速度が大きい。ま
た、水素透過膜ユニット５０の供給側は、水素放出側よ
りも圧力を高くする必要がある。このとき、薄い水素透
過膜５１のみでは圧力差により破損するので、水素透過
膜５１の一側を多孔質支持体５３によつて担持させ、機
械的強度を付与している。The permeation of H 2 in the hydrogen permeable membrane 51 utilizes the diffusion phenomenon, so that the permeation speed increases as the thickness in the permeation direction decreases and as the temperature increases to a predetermined high temperature. Further, the pressure on the supply side of the hydrogen permeable membrane unit 50 needs to be higher than that on the hydrogen release side. At this time, since only the thin hydrogen permeable membrane 51 is broken by the pressure difference, one side of the hydrogen permeable membrane 51 is supported by the porous support 53 to provide mechanical strength.
【０００７】更に、水素透過膜５１を薄くして水素透過
性能を向上させながら耐久性を確保するための多孔質支
持体５３には、所定の高温における耐酸化性が要求され
る。このため、多孔質支持体５３の材料として、セラミ
ックス、ガラス、ステンレス等の使用が検討されている
が、周囲部材との接合性や機械加工性などを考慮する
と、金属、特にステンレスが望ましい。Further, the porous support 53 for securing the durability while improving the hydrogen permeable performance by thinning the hydrogen permeable membrane 51 is required to have oxidation resistance at a predetermined high temperature. For this reason, the use of ceramics, glass, stainless steel, etc. as the material of the porous support 53 has been studied, but metals, particularly stainless steel, are desirable in consideration of the bonding property with peripheral members and the machinability.
【０００８】このような水素透過膜５１は、上述したよ
うに透過方向の厚さが薄いことが求められるが、水素以
外のガスの透過を防ぐ上からピンホールを含んでいない
ことが必要である。ピンホールを防止するための水素透
過膜５１の最低膜厚は、多孔質支持体５３の表面の孔径
に依存し、この孔径が大きいほどピンホールが生じ易く
なる。As described above, such a hydrogen permeable film 51 is required to have a small thickness in the permeation direction. However, it is necessary that the hydrogen permeable film 51 does not include a pinhole in order to prevent permeation of gases other than hydrogen. . The minimum thickness of the hydrogen permeable membrane 51 for preventing pinholes depends on the pore size on the surface of the porous support 53, and the larger the pore size, the more likely the occurrence of pinholes.
【０００９】多孔質支持体５３がガラス製の場合、例え
ば平均細孔径が３１０ｎｍのものを使用する報告があ
り、Ｐｄ製の水素透過膜５１の厚さは１３μｍである
（Ｃｈｅｍｉｓｔｒｙ Ｌｅｔｔｅｒｓ Ｎｏ．１０，
ｐｐ．１６８７−１６９０，１９８８）。これに対し、
ステンレスにて多孔質支持体５３を製作する場合、ステ
ンレスの粉末や繊維の焼結体において、平均細孔径を１
μｍ未満にすることは困難であるので、ガラス製の場合
よりも水素透過膜５１の膜厚が大きくならざるを得ず、
水素透過能が低下する。When the porous support 53 is made of glass, for example, it is reported to use one having an average pore diameter of 310 nm, and the thickness of the hydrogen-permeable membrane 51 made of Pd is 13 μm (Chemistry Letters No. 10, No. 10).
pp. 1687-1690, 1988). In contrast,
When the porous support body 53 is made of stainless steel, the average pore diameter of the sintered body of stainless steel powder or fiber is 1
Since it is difficult to reduce the thickness to less than μm, the thickness of the hydrogen-permeable film 51 must be larger than that of the case made of glass,
Hydrogen permeability decreases.
【００１０】一方、従来の水素透過膜は、このように水
素を選択的に透過させる薄膜として、Ｐｄ又はＰｄ合金
を使用するものが主であるが、Ｐｄに代わる合金などの
研究も行なわれている。On the other hand, conventional hydrogen permeable membranes mainly use Pd or a Pd alloy as a thin film for selectively permeating hydrogen as described above, but researches on alloys replacing Pd have been conducted. I have.
【００１１】特公平４−７４０４５公報、特公平５−７
９３６７公報、特公平６−９８２８１公報には、Ｐｄに
代えてＶ合金で構成させた水素透過膜５１について記載
されている。これらのＶ合金を数μｍオーダーまで薄膜
化することを考えた場合、延性の乏しさから圧延で薄膜
を作製することには困難を伴い、ＣＶＤ（気相化学反
応）、スパッタリングなどのドライプロセスにより、母
材となる多孔質支持体５３の表面に透過合金を析出させ
ることが有効な手法の一つと考えられる。ところで、こ
れらのＶ合金は、いずれも表面に水素透過の障害となる
酸化物を形成し易いことから、酸化を防止する目的でＰ
ｄ又はＰｄ合金を極薄く被覆させることについて言及し
ている。Japanese Patent Publication No. 4-74045, Japanese Patent Publication No. 5-7
No. 9367 and Japanese Patent Publication No. 6-98281 describe a hydrogen permeable film 51 made of a V alloy instead of Pd. When considering thinning these V alloys to the order of several μm, it is difficult to produce thin films by rolling due to poor ductility, and dry processes such as CVD (gas phase chemical reaction) and sputtering are required. Precipitating a permeable alloy on the surface of the porous support 53 serving as a base material is considered to be one of effective methods. By the way, since these V alloys all easily form oxides on the surface that hinder hydrogen permeation, P alloys are used for the purpose of preventing oxidation.
Reference is made to a very thin coating of d or Pd alloy.
【００１２】しかしながら、例えば多孔質支持体５３に
Ｐｄ又はＰｄ合金、非Ｐｄ合金、Ｐｄ又はＰｄ合金の順
にコーティングすることを考えた場合、図１２に模式的
に示すように多孔質支持体５３の多孔体粒子５３ａに薄
いＰｄ又はＰｄ合金５１ａが部分的に形成され、このＰ
ｄ又はＰｄ合金５１ａと非Ｐｄ合金５１ｂとが非接触の
箇所を生じ、非Ｐｄ合金５１ｂに露出箇所を生じるた
め、十分な耐酸化性を付与することができない。これの
防止のために、多孔体粒子５３ａに形成したＰｄ又はＰ
ｄ合金５１ａによつて非Ｐｄ合金５１ｂを完全に覆う場
合には、図１３に示すように多孔体粒子５３ａ上に形成
するＰｄ又はＰｄ合金５１ａが厚くなり、水素透過能が
低下するのみならず、高価なＰｄの使用量が増加するた
め、好ましくない。なお、非Ｐｄ合金５１ｂ上のＰｄ又
はＰｄ合金５１ｃは、平面上への加工になるため、薄く
形成できる。However, when coating the porous support 53 in the order of Pd or a Pd alloy, a non-Pd alloy, Pd or a Pd alloy, for example, as shown in FIG. A thin Pd or Pd alloy 51a is partially formed on the porous particles 53a.
Since d or the Pd alloy 51a and the non-Pd alloy 51b form a non-contact portion and an exposed portion occurs in the non-Pd alloy 51b, sufficient oxidation resistance cannot be imparted. To prevent this, Pd or Pd formed on the porous particles 53a
When the non-Pd alloy 51b is completely covered by the d alloy 51a, the Pd or Pd alloy 51a formed on the porous particles 53a becomes thick as shown in FIG. However, the amount of expensive Pd used is undesirably increased. Note that Pd or the Pd alloy 51c on the non-Pd alloy 51b can be formed thin because it is processed on a plane.
【００１３】このように、従来の水素透過膜５１は主と
してＰｄ又はＰｄ合金を材料としているが、水素透過性
能に劣り、所要の水素透過速度を確保するために大きな
膜面積を必要とし、結果として改質器も大きくならざる
を得ない。As described above, the conventional hydrogen permeable film 51 is mainly made of Pd or a Pd alloy, but is inferior in hydrogen permeation performance and requires a large film area to secure a required hydrogen permeation speed. The reformer must also be large.
【００１４】そこで、本発明は、Ｐｄ又はＰｄ合金など
の水素透過膜の薄膜化を可能とし、その使用量を削減し
た水素透過膜ユニット及び水素透過膜ユニットの製造方
法を提供し、その製作を容易かつ安価とすることを目的
としている。Therefore, the present invention provides a hydrogen permeable membrane unit and a method for manufacturing the hydrogen permeable membrane unit, which enable thinning of a hydrogen permeable membrane such as Pd or a Pd alloy, and reduce the amount of use thereof. It is intended to be easy and cheap.
【００１５】すなわち、本発明は、多孔質支持体５３の
表面に析出させる金属製の水素透過膜５１にピンホール
を生じさせることなく、薄膜化させた水素透過膜ユニッ
ト及びその製造方法の提供を目的としている。That is, the present invention provides a hydrogen permeable membrane unit which is thinned without forming a pinhole in the metal hydrogen permeable membrane 51 deposited on the surface of the porous support 53, and a method of manufacturing the same. The purpose is.
【００１６】[0016]
【課題を解決するための手段】本発明は、このような従
来の技術的課題に鑑みてなされたもので、その構成は、
次の通りである。請求項１の発明は、多孔質支持体４の
表面に接合させた水素透過膜２を有する水素透過膜ユニ
ットであつて、前記水素透過膜２が、多孔質支持体４に
含有させた穴埋材７の上に成膜させた後に該穴埋材７を
除去して形成されていることを特徴とする水素透過膜ユ
ニットである。請求項２の発明は、多孔質支持体４の表
面に接合させた水素透過膜２を有する水素透過膜ユニッ
トの製造方法であつて、多孔質支持体４の少なくとも表
層部に穴埋材７を含有させて表面の空孔を塞いだ後、該
多孔質支持体４及び穴埋材７の表面に水素透過膜２を成
膜させ、次いで、穴埋材７を除去することを特徴とする
水素透過膜ユニットの製造方法である。請求項３の発明
は、多孔質支持体４の表面に接合させた水素透過膜２を
有する水素透過膜ユニットの製造方法であつて、多孔質
支持体４の少なくとも表層部に穴埋材７を含有させて表
面の空孔を塞ぐと共に、多孔質支持体４の表面の穴埋材
（７）を除去して多孔体粒子４ａからなる凸部４ｂを形
成させた後、多孔質支持体４及び穴埋材７の表面に水素
透過膜２を成膜させ、次いで、穴埋材７を除去すること
を特徴とする水素透過膜ユニットの製造方法である。請
求項４の発明は、多孔質支持体４の表面に接合させた水
素透過膜２を有する水素透過膜ユニットの製造方法であ
つて、多孔質支持体４の表層部に研磨を施して研磨片か
らなる肉薄部分４ｃを形成し、該肉薄部分４ｃによつて
表面の空孔を大略塞いで平滑状平面を形成させた後、該
多孔質支持体４の表面に水素透過膜２を成膜させ、次い
で、腐食液に浸して肉薄部分４ｃを除去することを特徴
とする水素透過膜ユニットの製造方法である。請求項５
の発明は、水素透過膜２が、非Ｐｄ合金２ｂの表裏両面
を白金族元素又はその合金２ａ，２ｃによつてコーティ
ングして形成されていることを特徴とする請求項２，３
又は４の水素透過膜ユニットの製造方法である。SUMMARY OF THE INVENTION The present invention has been made in view of such a conventional technical problem.
It is as follows. The invention according to claim 1 is a hydrogen permeable membrane unit having a hydrogen permeable membrane 2 joined to the surface of a porous support 4, wherein the hydrogen permeable membrane 2 is filled in a porous support 4. A hydrogen permeable membrane unit formed by forming a film on a material 7 and removing the filling material 7. The invention according to claim 2 is a method for producing a hydrogen permeable membrane unit having a hydrogen permeable membrane 2 bonded to the surface of a porous support 4, wherein a hole filling material 7 is provided on at least a surface layer of the porous support 4. After filling the pores on the surface to contain the hydrogen, a hydrogen permeable film 2 is formed on the surfaces of the porous support 4 and the hole filling material 7, and then the hydrogen filling material 7 is removed. It is a manufacturing method of a permeable membrane unit. The invention according to claim 3 is a method for manufacturing a hydrogen permeable membrane unit having a hydrogen permeable membrane 2 bonded to the surface of a porous support 4, wherein a hole filling material 7 is provided on at least a surface layer of the porous support 4. After filling the pores on the surface and removing the hole filling material (7) on the surface of the porous support 4 to form the projections 4b made of the porous particles 4a, the porous support 4 A method for manufacturing a hydrogen permeable membrane unit, comprising forming a hydrogen permeable film 2 on the surface of a filling material 7 and then removing the filling material 7. The invention according to claim 4 is a method for manufacturing a hydrogen permeable membrane unit having a hydrogen permeable membrane 2 bonded to the surface of a porous support 4, wherein the surface layer of the porous support 4 is polished to obtain a polishing piece. A thin portion 4c is formed, and the thin portion 4c substantially closes the pores on the surface to form a smooth flat surface. Then, the hydrogen permeable film 2 is formed on the surface of the porous support 4. And then removing the thin portion 4c by immersion in a corrosive liquid. Claim 5
The invention according to claim 2, wherein the hydrogen permeable membrane 2 is formed by coating the front and back surfaces of the non-Pd alloy 2b with a platinum group element or its alloys 2a, 2c.
Or a method for manufacturing a hydrogen permeable membrane unit of 4.
【００１７】[0017]
【発明の実施の形態】以下、本発明の実施の形態につい
て図面を参照して説明する。図１，図２は、本発明に係
る水素透過膜ユニットの第１実施の形態を示す。図１は
水素透過膜ユニット１を示し、従来例と実質的に同様の
構成部材を有している。すなわち、水素透過膜ユニット
１は、Ｐｄ又はＰｄ合金製の水素透過膜２を有し、この
水素透過膜２が、金属からなる枠体３及び多孔質支持体
４の内の少なくとも一方に、接合部５によつて接合され
ている。接合部５は、多孔質支持体４の上に、メッキ、
ＣＶＤ（気相化学反応）、スパッタリング、イオンプレ
ーティング、蒸着などの方法によつて水素透過膜２を形
成することで、同時に形成される。多孔質支持体４は、
セラミックス、ガラス、ステンレス等の粉末や繊維の焼
結体、好ましくは金属、特にステンレスの粉末や繊維の
焼結体であり、水素透過のための連通孔からなる細い空
孔を有している。枠体３と多孔質支持体４とは、リーク
を生じないように溶接、ろう付けなどによつて接合さ
れ、接合部６を有している。Embodiments of the present invention will be described below with reference to the drawings. 1 and 2 show a hydrogen permeable membrane unit according to a first embodiment of the present invention. FIG. 1 shows a hydrogen permeable membrane unit 1 having substantially the same components as those of the conventional example. That is, the hydrogen permeable membrane unit 1 has a hydrogen permeable membrane 2 made of Pd or a Pd alloy, and this hydrogen permeable membrane 2 is bonded to at least one of the metal frame 3 and the porous support 4. It is joined by a part 5. The bonding portion 5 is formed by plating on the porous support 4,
The hydrogen permeable film 2 is formed at the same time by forming the hydrogen permeable film 2 by a method such as CVD (gas phase chemical reaction), sputtering, ion plating, or vapor deposition. The porous support 4 is
It is a sintered body of powder or fiber of ceramics, glass, stainless steel or the like, preferably a sintered body of powder or fiber of metal, particularly stainless steel, and has fine pores formed of communication holes for hydrogen permeation. The frame 3 and the porous support 4 are joined by welding, brazing or the like so as not to cause a leak, and have a joint 6.
【００１８】水素透過膜ユニット１の製造に際しては、
予め、多孔質支持体４の少なくとも表層部に穴埋材７を
含有させ、多孔質支持体４の表面の空孔を穴埋材７によ
つて塞ぐ。その後、この多孔質支持体４及び穴埋材７の
上に水素透過膜２を成膜・接合させ、その後に穴埋材７
を除去し、水素透過のための連通孔を復活させる。な
お、図２の多孔質支持体４は、焼結体の表面に位置する
多孔体粒子４ａのみを示し、他の多孔体粒子４ａは省略
してある。In manufacturing the hydrogen permeable membrane unit 1,
The hole-filling material 7 is contained at least in the surface layer of the porous support 4 in advance, and pores on the surface of the porous support 4 are closed by the hole-filling material 7. After that, the hydrogen permeable membrane 2 is formed and bonded on the porous support 4 and the hole filling material 7.
Is removed, and the communication hole for hydrogen permeation is restored. Note that the porous support 4 in FIG. 2 shows only the porous particles 4a located on the surface of the sintered body, and the other porous particles 4a are omitted.
【００１９】具体的には、多孔質支持体４の表層部に穴
埋材７である樹脂を含有させ、細孔を塞いでほぼ平滑面
を形成させ、必要に応じて穴埋材７を含有する多孔質支
持体４の表面を平滑に削成した後、水素透過金属からな
る水素透過膜２を成膜させる。穴埋材７は、溶融状態の
ものを塗布などの手段によつて多孔質支持体４に含有さ
せ、硬化させることで形成することができ、多孔質支持
体４よりも低融点のものが望ましい。水素透過膜２を成
膜させた後、穴埋材７を除去して多孔質支持体４の連通
孔を復活させる。穴埋材７が樹脂からなる場合には、穴
埋材７を有する多孔質支持体４及び水素透過膜２を適当
な有機溶剤中に浸し、穴埋材７を溶融除去させる。ま
た、穴埋材７が熱可塑性樹脂からなる場合には、穴埋材
７を有する多孔質支持体４及び水素透過膜２を加熱し、
穴埋材７を溶融除去させることもできる。Specifically, a resin which is a filling material 7 is contained in the surface layer of the porous support 4 to form a substantially smooth surface by closing the pores, and the filling material 7 is contained if necessary. After smoothing the surface of the porous support 4 to be formed, a hydrogen-permeable film 2 made of a hydrogen-permeable metal is formed. The filling material 7 can be formed by incorporating a material in a molten state into the porous support 4 by means of coating or the like and curing the material. A material having a melting point lower than that of the porous support 4 is desirable. . After the hydrogen permeable membrane 2 is formed, the hole filling material 7 is removed, and the communication holes of the porous support 4 are restored. When the filling material 7 is made of resin, the porous support 4 having the filling material 7 and the hydrogen permeable membrane 2 are immersed in an appropriate organic solvent to melt and remove the filling material 7. When the filling material 7 is made of a thermoplastic resin, the porous support 4 having the filling material 7 and the hydrogen permeable membrane 2 are heated,
The hole filling material 7 can be melted and removed.
【００２０】これにより、ほぼ平滑面にした多孔質支持
体４の表面に水素透過膜２を成膜させることになるの
で、多孔質支持体４の上に薄い水素透過膜２を成膜させ
ながら、水素透過膜２にピンホールが形成されることを
防止することができる。すなわち、水素透過膜２に、多
孔質支持体４の細孔を埋めるための膜厚を与える必要が
なく、目的に沿つた必要最小限の膜厚で均一にコーティ
ングすることができる。水素透過金属である水素透過膜
２の膜厚は、水素透過膜ユニット１をメンブレンリアク
タに組み込み、メンブレンリアクタを運転させる際に負
荷される圧力に対して、膜が多孔質支持体４の空孔部分
で破損しない強度を保てる程度でよい。As a result, the hydrogen permeable film 2 is formed on the surface of the porous support 4 having a substantially smooth surface, so that the thin hydrogen permeable film 2 is formed on the porous support 4 In addition, it is possible to prevent pinholes from being formed in the hydrogen permeable film 2. That is, there is no need to provide the hydrogen permeable membrane 2 with a film thickness for filling the pores of the porous support 4, and it is possible to uniformly coat the hydrogen permeable film 2 with a minimum necessary film thickness for the purpose. The thickness of the hydrogen permeable membrane 2, which is a hydrogen permeable metal, depends on the pressure applied when the hydrogen permeable membrane unit 1 is incorporated into the membrane reactor and the membrane reactor is operated. It only needs to be strong enough not to break at the part.
【００２１】図３は、水素透過膜２の他の構造例を示
し、水素透過膜２が、Ｐｄ又はＰｄ合金２ａ、非Ｐｄ合
金２ｂ及びＰｄ又はＰｄ合金２ｃの３層構造を有してい
る。この場合にも、多孔質支持体４の表面に水素透過膜
２を形成する前に、樹脂からなる穴埋材７を塗布などの
手段によつて含浸させ、金属多孔体である多孔質支持体
４の孔を塞ぎ、多孔質支持体４の一側表面を平滑な状態
にする。FIG. 3 shows another example of the structure of the hydrogen permeable film 2. The hydrogen permeable film 2 has a three-layer structure of Pd or Pd alloy 2a, non-Pd alloy 2b and Pd or Pd alloy 2c. . Also in this case, before the hydrogen permeable membrane 2 is formed on the surface of the porous support 4, a hole filling material 7 made of resin is impregnated by means such as coating to form a porous support made of a porous metal. The pores of No. 4 are closed, and one surface of the porous support 4 is made smooth.
【００２２】続いて、穴埋材７を含有させた多孔質支持
体４の平滑表面上に、水素透過膜２を形成させる。水素
透過膜２は、Ｐｄ又はＰｄ合金２ａ、非Ｐｄ合金２ｂ、
Ｐｄ又はＰｄ合金２ｃの順に成膜させる。このようにし
て水素透過膜２を接合させた多孔質支持体４は、穴埋材
７の種類に応じた所要の手段、つまり、加熱、溶剤の塗
布等の手段により、穴埋材７を除去する。穴埋材７の除
去は、減圧環境下で行なうこともできる。Subsequently, the hydrogen permeable membrane 2 is formed on the smooth surface of the porous support 4 containing the filling material 7. The hydrogen permeable membrane 2 is made of Pd or a Pd alloy 2a, a non-Pd alloy 2b,
Pd or a Pd alloy 2c is formed in this order. The porous support 4 to which the hydrogen permeable membrane 2 has been bonded in this manner is used to remove the hole filling material 7 by a necessary means according to the type of the hole filling material 7, that is, by heating, applying a solvent, or the like. I do. The removal of the filling material 7 can also be performed under a reduced pressure environment.
【００２３】この構造例によれば、水素透過膜２を、多
孔質支持体４の孔が穴埋材７によつて塞がれて平滑表面
をなしている状態で形成させるため、特にＰｄ又はＰｄ
合金２ａに孔を埋めるための膜厚を与える必要はなく、
目的に沿つた必要最小限の膜厚でコーティングすること
ができる。すなわち、図３に示す水素透過膜２では、非
Ｐｄ合金２ｂに耐酸化性を付与できる程度のＰｄ又はＰ
ｄ合金２ａ，２ｃの膜厚でよい。水素透過膜ユニット１
をメンブレンリアクタに組み込み、メンブレンリアクタ
を運転させる際に負荷される圧力に対しては、Ｐｄ又は
Ｐｄ合金２ａ、非Ｐｄ合金２ｂ及びＰｄ又はＰｄ合金２
ｃの３層構造によつて対抗することになる。なお、薄層
をなすＰｄ又はＰｄ合金２ａ，２ｃは、耐酸化性と水素
分子の解離性（触媒能）と水素透過能とが備わつていれ
ばよく、Ｐｄを含む白金族元素（Ｒｕ，Ｒｈ，Ｏｓ，Ｉ
ｒ，Ｐｔ）及びその合金を広く使用することが可能であ
る。According to this structural example, the hydrogen permeable membrane 2 is formed in a state where the pores of the porous support 4 are closed by the hole filling material 7 to form a smooth surface. Pd
There is no need to give the alloy 2a a film thickness to fill the holes,
Coating can be performed with the minimum necessary film thickness according to the purpose. That is, in the hydrogen-permeable film 2 shown in FIG. 3, Pd or Pd is sufficient to provide the non-Pd alloy 2b with oxidation resistance.
The thickness of the d alloys 2a and 2c may be sufficient. Hydrogen permeable membrane unit 1
Is incorporated in the membrane reactor, and Pd or Pd alloy 2a, non-Pd alloy 2b and Pd or Pd alloy 2 are applied to the pressure applied when operating the membrane reactor.
c. The thin layer of Pd or the Pd alloys 2a and 2c only needs to have oxidation resistance, hydrogen molecule dissociation (catalytic ability) and hydrogen permeability, and a platinum group element containing Pd (Ru , Rh, Os, I
(r, Pt) and its alloys can be widely used.
【００２４】図４〜図７は、本発明に係る水素透過膜ユ
ニット１の第２実施の形態を示し、第１実施の形態と同
一部分には同一符号を付してある。第２実施の形態にあ
つては、図４に示すように多孔質支持体４に穴埋材７を
含浸させた後、図５に示すように多孔質支持体４の表面
に多孔体粒子４ａからなる僅かな凸部４ｂを形成させ、
その後、図６に示すように凸部４ｂの上に水素透過膜２
を成膜させ、図７に示すように穴埋材７を除去してい
る。従つて、第１実施の形態と比較して、水素透過膜２
との接合部５が凸部４ｂに広く形成されている。この水
素透過膜２は、図７に示すように例えばＰｄ又はＰｄ合
金２ａ、非Ｐｄ合金２ｂ及びＰｄ又はＰｄ合金２ｃの３
層構造を有している。この多孔質支持体４の上に形成す
るＰｄ又はＰｄ合金２ａは、非Ｐｄ合金２ｂに耐酸化性
を付与するように形成させればよく、非Ｐｄ合金２ｂに
露出箇所を生じさせない程度に薄く形成させることがで
きる。これにより、多孔体粒子４ａの凸部４ｂと水素透
過膜２との凹凸係合によるアンカー効果が生じるので、
水素透過膜２の耐剥離性が向上する。なお、凸部４ｂ
が、Ｐｄ又はＰｄ合金２ａのみならず非Ｐｄ合金２ｂに
対しても凹凸係合する状態にすれば、アンカー効果が良
好に生じる。FIGS. 4 to 7 show a second embodiment of the hydrogen permeable membrane unit 1 according to the present invention, and the same parts as those in the first embodiment are denoted by the same reference numerals. In the second embodiment, after the porous support 4 is impregnated with the hole filling material 7 as shown in FIG. 4, the porous particles 4a are formed on the surface of the porous support 4 as shown in FIG. A slight convex portion 4b made of
After that, as shown in FIG.
Is formed, and the hole filling material 7 is removed as shown in FIG. Therefore, as compared with the first embodiment, the hydrogen permeable membrane 2
Is widely formed on the projection 4b. As shown in FIG. 7, this hydrogen permeable film 2 is made of, for example, Pd or Pd alloy 2a, non-Pd alloy 2b and Pd or Pd alloy 2c.
It has a layered structure. The Pd or Pd alloy 2a formed on the porous support 4 may be formed so as to impart oxidation resistance to the non-Pd alloy 2b, and is thin enough not to cause an exposed portion in the non-Pd alloy 2b. Can be formed. As a result, an anchor effect is generated due to the concave-convex engagement between the convex portions 4b of the porous particles 4a and the hydrogen permeable membrane 2, so that
The peel resistance of the hydrogen permeable film 2 is improved. The protrusion 4b
However, the anchor effect can be satisfactorily generated if the uneven engagement is performed not only with Pd or the Pd alloy 2a but also with the non-Pd alloy 2b.
【００２５】ところで、非Ｐｄ合金２ｂとしてＴａを使
用する場合、Ｔａは、水素透過能に優れているが、耐水
素脆性に乏しい。本発明者等は、Ｔａに、水素化物生成
を抑制させる効果があるＦｅ及びＭｏの内の少なくとも
１種の金属元素を添加金属として添加することにより、
Ｔａの水素透過能の低下を僅かな量に抑えつつ、耐水素
脆性が向上することを見いだした。これらの添加金属の
添加量が少量では、十分な水素化物抑制効果が認められ
ないことから、添加量が５原子％以上、好ましくは下限
が１０原子％であることが望ましい。一方、これらの添
加は、透過能を低下させる効果を有することから、大量
添加は水素透過能を著しく減少させる。そこで、Ｆｅ又
はＭｏのＴａへの添加量は、７０原子％以下、好ましく
は上限が６０原子％であることが望ましい。When Ta is used as the non-Pd alloy 2b, Ta has excellent hydrogen permeability, but poor hydrogen embrittlement resistance. By adding at least one metal element of Fe and Mo, which has an effect of suppressing hydride generation, to Ta as an additional metal,
It has been found that the hydrogen embrittlement resistance is improved while suppressing the decrease in the hydrogen permeability of Ta to a small amount. If the addition amount of these additional metals is small, a sufficient hydride suppression effect is not recognized, so that the addition amount is desirably 5 atomic% or more, and preferably the lower limit is 10 atomic%. On the other hand, since these additions have the effect of lowering the permeability, a large amount of addition significantly reduces the hydrogen permeability. Therefore, the amount of Fe or Mo added to Ta is desirably 70 atomic% or less, and preferably has an upper limit of 60 atomic%.
【００２６】このようなＴａをベース金属とし、Ｆｅ及
びＭｏの内の少なくとも１種の金属元素を添加したＴａ
合金を用いる水素透過膜２によれば、水素透過性と耐水
素脆化性とを両立させることが可能である。加えて、Ｔ
ａ、Ｆｅ及びＭｏは、いずれもＰｄ合金よりも材料単価
が非常に低廉かつ入手容易であるため、水素透過膜２を
安価かつ十分に供給することが可能になる。なお、Ｔａ
にＦｅ及びＭｏの内の少なくとも１種を添加すると、い
ずれの場合においても水素透過係数は減少するものの、
冷却時における割れの発生が抑制される。水素透過膜２
に、Ｔａをベース金属とし、Ｆｅ及びＭｏの内の少なく
とも１種の金属元素を添加したＴａ合金を用いることに
より、Ｐｄ又はＰｄ合金とほぼ同等又はそれ以上に水素
透過性又は耐水素脆化性に優れる水素透過膜を得ること
ができる。[0026] Such Ta is used as a base metal, and Ta added with at least one metal element of Fe and Mo is used.
According to the hydrogen permeable film 2 using an alloy, it is possible to achieve both hydrogen permeability and hydrogen embrittlement resistance. In addition, T
Since a, Fe, and Mo are all very inexpensive and easily available as compared with the Pd alloy, it is possible to supply the hydrogen permeable membrane 2 at low cost and sufficiently. In addition, Ta
When at least one of Fe and Mo is added to, the hydrogen permeability coefficient decreases in any case,
Generation of cracks during cooling is suppressed. Hydrogen permeable membrane 2
By using Ta as a base metal and using a Ta alloy to which at least one metal element of Fe and Mo is added, hydrogen permeability or hydrogen embrittlement resistance is substantially equal to or more than Pd or a Pd alloy. And a hydrogen permeable membrane having excellent heat resistance can be obtained.
【００２７】なお、図３に示すように水素透過膜２が非
Ｐｄ合金を含んで３層をなす場合、つまりＰｄ又はＰｄ
合金２ａ、非Ｐｄ合金２ｂ及びＰｄ又はＰｄ合金２ｃを
有する場合には、多孔体粒子４ａの凸部４ｂがＰｄ又は
Ｐｄ合金２ａにのみ凹凸係合するよりも、多孔質支持体
４側のＰｄ又はＰｄ合金２ａ膜を形成した状態におい
て、凸部４ｂがＰｄ又はＰｄ合金２ａの表面から露出す
る程度の大きさに凸部４ｂを形成し、その上に非Ｐｄ合
金２ｂを成膜させ、凸部４ｂと非Ｐｄ合金２ｂとを凹凸
係合させることが望まれる。これにより、多孔体粒子４
ａの凸部４ｂと非Ｐｄ合金２ｂとの凹凸係合によるアン
カー効果が良好に生じるので、水素透過膜２の耐剥離性
を向上させることができる。As shown in FIG. 3, when the hydrogen permeable film 2 is made of three layers including a non-Pd alloy, that is, Pd or Pd
In the case of having the alloy 2a, the non-Pd alloy 2b and the Pd or Pd alloy 2c, the Pd on the porous support 4 side is larger than the protrusions 4b of the porous particles 4a are engaged with the Pd or Pd alloy 2a only. Alternatively, in a state where the Pd alloy 2a film is formed, the convex portion 4b is formed in such a size that the convex portion 4b is exposed from the surface of the Pd or the Pd alloy 2a, and the non-Pd alloy 2b is formed thereon. It is desired that the portion 4b and the non-Pd alloy 2b be engaged in a concave and convex manner. Thereby, the porous material particles 4
Since the anchor effect is favorably generated by the concave-convex engagement between the convex portion 4b and the non-Pd alloy 2b, the peeling resistance of the hydrogen-permeable film 2 can be improved.
【００２８】[0028]
【実施例】〔実施例１〕母材に平均細孔径１μｍのステ
ンレス多孔体を準備し、このステンレス製の多孔質支持
体４の表層部に樹脂を含浸させ、穴埋材７とした。その
後、研磨により、多孔質支持体４の表面の余分な樹脂を
除去し、この多孔質支持体４の表面に、Ｐｄ、Ｔａ（非
Ｐｄ合金）、Ｐｄの順にスパッタリング法により表１に
示す厚さにコーティングを行い、図３に示すものと同様
の構造の水素透過膜２を形成させた。コーティングの
後、真空中で加熱して樹脂を溶融除去させ、試料ｉを作
製した。EXAMPLES Example 1 A porous stainless steel body having an average pore diameter of 1 μm was prepared as a base material, and a resin was impregnated into the surface layer of the porous support 4 made of stainless steel to obtain a hole filling material 7. Thereafter, excess resin on the surface of the porous support 4 is removed by polishing, and Pd, Ta (non-Pd alloy), and Pd are deposited on the surface of the porous support 4 in this order by a sputtering method. Then, coating was performed to form a hydrogen permeable membrane 2 having the same structure as that shown in FIG. After the coating, the resin was melted and removed by heating in a vacuum to prepare a sample i.
【００２９】また、比較例ｉ，ｉｉとして、同様の多孔
質支持体４に穴埋材７を含浸させずに、Ｐｄ、Ｔａ（非
Ｐｄ合金）、Ｐｄからなる金属透過膜をそれぞれ表１に
示す厚さにコーティングした比較試料ｉ，ｉｉを用意し
た。As Comparative Examples i and ii, metal permeable membranes made of Pd, Ta (non-Pd alloy), and Pd without impregnating the same porous support 4 with the hole filling material 7 are shown in Table 1, respectively. Comparative samples i and ii coated to the indicated thickness were prepared.
【００３０】これらの試料ｉ及び比較試料ｉ，ｉｉを水
素透過試験装置に設置し、５００℃における水素透過速
度を測定したところ、実施例１に係る試料ｉに関しては
表１に示す値（１３０ｃｍ3 ／ｃｍ2 ／ｍｉｎ）が得ら
れた。These sample i and comparative samples i and ii were set in a hydrogen permeation test apparatus, and the hydrogen permeation rate at 500 ° C. was measured. As for sample i according to Example 1, the value shown in Table 1 (130 cm 3) was obtained. / Cm 2 / min).
【００３１】 〔表１〕 試料名 ： 実施例１（樹脂埋め有り） 透過膜厚さ： Ｐｄ：50ｎｍ＋Ｔａ：10μｍ＋Ｐｄ：50ｎｍ 透過速度 ： １３０ｃｍ3 ／ｃｍ2 ／ｍｉｎ 試料名 ： 比較例ｉ（樹脂埋め無し） 透過膜厚さ： Ｐｄ：50ｎｍ＋Ｔａ：10μｍ＋Ｐｄ：50ｎｍ 透過速度 ： リーク有り 試料名 ： 比較例ｉｉ（樹脂埋め無し） 透過膜厚さ： Ｐｄ：50ｎｍ＋Ｔａ：30μｍ＋Ｐｄ：50ｎｍ 透過速度 ： 透過せず [Table 1] Sample name: Example 1 (with resin filling) Transmission film thickness: Pd: 50 nm + Ta: 10 μm + Pd: 50 nm Transmission speed: 130 cm 3 / cm 2 / min Sample name: Comparative example i (without resin filling) ) Transmission film thickness: Pd: 50 nm + Ta: 10 μm + Pd: 50 nm Transmission speed: Leaked Sample name: Comparative example ii (without resin filling) Transmission film thickness: Pd: 50 nm + Ta: 30 μm + Pd: 50 nm Transmission speed: No transmission
【００３２】比較例ｉに係る比較試料ｉについては、透
過試験前のＨｅを用いた膜のリークチェックにより、リ
ークが認められた。この比較試料ｉでは、金属透過膜の
コーティング前の穴埋材７の形成を行なわなかつたた
め、多孔質支持体４の空孔が薄い金属透過膜（Ｐｄ、Ｔ
ａ、Ｐｄ）によつて完全には塞がらなかつたものと推定
される。また、比較試料ｉｉに関しては、Ｈｅのリーク
は認められなかつたものの、水素透過が生じなかつた。
これは、Ｐｄが５０ｎｍと薄いために、図１２に示すも
のと同様に、多孔質支持体４側においてＰｄ（Ｐｄ又は
Ｐｄ合金５１ａ）とＴａ（非Ｐｄ合金５１ｂ）が接触し
ない箇所を生じ、このＴａ（非Ｐｄ合金５１ｂ）の露出
部位においてＴａが酸化されて透過能が消失したものと
考えられる。As for the comparative sample i according to the comparative example i, a leak was confirmed by a leak check of the film using He before the transmission test. In this comparative sample i, since the hole filling material 7 was not formed before coating with the metal permeable membrane, the pores of the porous support 4 were thin and the metal permeable membrane (Pd, T
a, Pd), it is presumed that it was not completely closed. Further, for the comparative sample ii, although He leakage was not observed, hydrogen permeation did not occur.
Since Pd is as thin as 50 nm, as in the case shown in FIG. 12, a portion where Pd (Pd or Pd alloy 51a) and Ta (non-Pd alloy 51b) do not come into contact on the porous support 4 side is generated. It is considered that Ta was oxidized at the exposed portion of the Ta (non-Pd alloy 51b), and the permeability was lost.
【００３３】〔実施例２〕実施例１と同様に、多孔質支
持体４の表面の余分な樹脂からなる穴埋材７を除去した
後、多孔質支持体４の表面にスパッタリングエッチング
を行なつた。樹脂はステンレスよりもエッチング率が大
きく、多量に飛散（蒸発）するので、穴埋材７を選択的
に除去することが可能である。このようにして、穴埋材
７を僅かに除去して多孔体表面、つまり多孔質支持体４
の表面の多孔体粒子４ａに凸部４ｂを生じさせ、その
後、Ｐｄ、非Ｐｄ合金２ｂとしてのＴａ、Ｐｄの順に実
施例１と同様に成膜させて水素透過膜２を形成させ、試
料ｉｉｉを製作した。また、比較例ｉｉｉとして、凸部
４ｂを有しない点でのみ試料ｉｉｉと相違する比較試料
ｉｉｉ、つまり凸部４ｂを生じさせないで水素透過膜２
を成膜させた実施例１と同様の比較試料ｉｉｉを用意し
た。Example 2 In the same manner as in Example 1, the surface of the porous support 4 was subjected to sputtering etching after removing the excess resin filling material 7 made of resin from the surface of the porous support 4. Was. Since the resin has a higher etching rate than stainless steel and scatters (evaporates) in a large amount, the hole filling material 7 can be selectively removed. In this manner, the hole filling material 7 is slightly removed, and the surface of the porous body, that is, the porous support 4 is removed.
Then, a convex portion 4b is formed on the porous particles 4a on the surface of Pd, and then a film of Pd, Ta as the non-Pd alloy 2b, and Pd are formed in this order in the same manner as in Example 1 to form the hydrogen permeable film 2, and the sample iii Was made. Further, as Comparative Example iii, a comparative sample iii which is different from Sample iii only in that it does not have the convex portion 4b, that is, the hydrogen permeable membrane 2 having no convex portion 4b.
A comparative sample iii similar to that of Example 1 in which was formed into a film was prepared.
【００３４】これらの試料ｉｉｉ及び比較試料ｉｉｉに
ついて、水素吸蔵・放出試験を繰り返し行なつた。その
結果、前者における膜が剥離するまでの繰り返し回数
は、後者を上回り、凸部４ｂの積極的な形成により耐剥
離性が向上することが認められた。A hydrogen storage / release test was repeatedly performed on these sample iii and comparative sample iii. As a result, it was recognized that the number of repetitions until the film was peeled in the former exceeded that of the latter, and that the peeling resistance was improved by the active formation of the projections 4b.
【００３５】図８〜図１０は、本発明に係る水素透過膜
ユニット１の第３実施の形態を示し、第１実施の形態と
同一部分には同一符号を付してある。第３実施の形態に
あつては、先ず、図８に示すように多孔質支持体４の表
面を研磨し、多孔質支持体４の表面の空孔を多孔質支持
体４の多孔体粒子４ａの研磨片からなる肉薄部分４ｃに
よつてほぼ塞ぎ、平滑状平面を形成させる。肉薄部分４
ｃは、研磨することにより、多孔質支持体４の表層の一
部が潰れて塑性変形した肉薄の研磨片を生じて形成され
る。その後、この多孔質支持体４の平滑状平面をなす表
面上に、図９に示すように水素透過膜２を成膜・接合さ
せる。この水素透過膜２は、非Ｐｄ合金２ｂに相当する
Ｔａ若しくはその合金の両面を白金族元素若しくはその
合金（２ａ，２ｃ）で挟んだものであり、図３に示すも
のと同様にサンドイッチ状をなしている。FIGS. 8 to 10 show a third embodiment of the hydrogen permeable membrane unit 1 according to the present invention, and the same parts as those in the first embodiment are denoted by the same reference numerals. In the third embodiment, first, as shown in FIG. 8, the surface of the porous support 4 is polished to remove pores on the surface of the porous support 4 so that the porous particles 4a of the porous support 4 are removed. This is almost closed by the thin portion 4c made of the polishing piece to form a smooth flat surface. Thin part 4
By polishing, part of the surface layer of the porous support 4 is crushed to form a thin polished piece plastically deformed. Thereafter, a hydrogen permeable membrane 2 is formed and bonded on the surface of the porous support 4 which forms a smooth flat surface, as shown in FIG. This hydrogen permeable membrane 2 is formed by sandwiching both sides of Ta corresponding to the non-Pd alloy 2b or an alloy thereof with a platinum group element or an alloy thereof (2a, 2c), and has a sandwich shape as shown in FIG. No.
【００３６】次に、水素透過膜２を成膜させた多孔質支
持体４を腐食液に浸し、肉薄部分４ｃを溶解させて除去
し、水素透過のための連通孔を復活させる。水素透過膜
２は、多孔体粒子４ａの表面に接合されたままである。
腐食液は、水洗して除去させる。多孔質支持体４をステ
ンレス鋼によつて製作し、多孔質支持体４に接する透過
膜を白金族元素又は白金族元素を含んだ合金によつて製
作すれば、この透過膜の耐腐食性が良好なため、腐食液
によつて侵され難い。このため、肉薄部分４ｃが、多孔
体粒子４ａに比して早期に溶解・除去される。従つて、
腐食液は、多孔質支持体４を早期又は選択的に溶解さ
せ、多孔質支持体４に接合する水素透過膜２を溶解させ
難い液体であればよく、多孔質支持体４及び水素透過膜
２の材料に応じて、王水、希硝酸などが使用される。Next, the porous support 4 on which the hydrogen permeable membrane 2 has been formed is immersed in a corrosive liquid to dissolve and remove the thin portion 4c, thereby restoring the communication hole for hydrogen permeation. The hydrogen permeable membrane 2 remains bonded to the surface of the porous particles 4a.
The etchant is removed by washing with water. If the porous support 4 is made of stainless steel and the permeable membrane in contact with the porous support 4 is made of a platinum group element or an alloy containing a platinum group element, the corrosion resistance of the permeable membrane is reduced. Good, not easily attacked by corrosive liquids. For this reason, the thin portion 4c is dissolved and removed earlier than the porous particles 4a. Therefore,
The etchant may be any liquid that dissolves the porous support 4 early or selectively and hardly dissolves the hydrogen permeable membrane 2 bonded to the porous support 4. Aqua regia, diluted nitric acid, and the like are used depending on the material used.
【００３７】[0037]
【発明の効果】以上の説明によつて理解されるように、
本発明に係る水素透過膜ユニット及びその製造方法によ
れば、次の効果を奏することができる。請求項１〜５に
係る発明によれば、Ｐｄ又はＰｄ合金を含む白金族元素
又はその合金などの水素透過膜を薄膜化させ、その使用
量を削減することができる。これにより、水素透過膜の
製作、ひいては水素透過膜ユニットの製作を容易かつ安
価とすることができる。As will be understood from the above description,
According to the hydrogen permeable membrane unit and the method of manufacturing the same according to the present invention, the following effects can be obtained. According to the first to fifth aspects of the present invention, the hydrogen-permeable film made of a platinum group element containing Pd or a Pd alloy or an alloy thereof can be made thinner, and the amount of use thereof can be reduced. This makes it easy and inexpensive to manufacture the hydrogen permeable membrane and thus the hydrogen permeable membrane unit.
【００３８】加えて、請求項１〜３に係る発明によれ
ば、多孔質支持体の少なくとも表層部に穴埋材を含有さ
せて表面の空孔を塞いだ後、多孔質支持体の表面に水素
透過膜を成膜させ、次いで、穴埋材を除去する。このよ
うに、多孔質支持体の孔を穴埋材によつて埋めて事実上
の平滑面を形成した後に水素透過膜を成膜させるので、
ピンホールを防止しながら、水素透過膜の厚さを必要最
小限に抑えることができる。その結果、水素透過膜ユニ
ットの水素透過能が向上するのみならず、成膜に使用す
る材料を削減して、重量を低減させることができる。In addition, according to the first to third aspects of the present invention, at least the surface layer portion of the porous support is filled with a hole filling material to close the pores on the surface, and then the surface of the porous support is A hydrogen permeable film is formed, and then the hole filling material is removed. As described above, the hydrogen permeable membrane is formed after the pores of the porous support are filled with the hole filling material to form a practically smooth surface.
The thickness of the hydrogen permeable membrane can be minimized while preventing pinholes. As a result, not only can the hydrogen permeability of the hydrogen permeable membrane unit be improved, but also the material used for film formation can be reduced and the weight can be reduced.
【００３９】請求項３に係る発明によれば、更に、多孔
質支持体の表面の穴埋材を一部除去して多孔体粒子から
なる凸部を形成させた後、多孔質支持体及び穴埋材の表
面に水素透過膜を成膜させるので、水素透過膜が多孔質
支持体に凹凸係合した状態になり、水素透過膜の耐剥離
性が向上する。その結果、多孔質支持体と水素透過膜と
の熱膨張差に起因する剥離が抑制され、材料に制限を受
け難くなると共に、水素透過膜ユニットの耐久性が向上
する。特に、水素透過膜が水素吸蔵性能を有する金属に
て製作されている場合には、水素吸蔵時に体積膨張を生
ずるが、これに起因する剥離も抑制されることになり、
水素透過膜ユニットの耐久性が著しく向上する。According to the third aspect of the present invention, after the hole filling material on the surface of the porous support is partially removed to form a projection made of porous particles, the porous support and the hole are removed. Since the hydrogen permeable film is formed on the surface of the filling material, the hydrogen permeable film is in a state of being unevenly engaged with the porous support, and the peeling resistance of the hydrogen permeable film is improved. As a result, peeling due to the difference in thermal expansion between the porous support and the hydrogen permeable membrane is suppressed, the material is not easily restricted, and the durability of the hydrogen permeable membrane unit is improved. In particular, when the hydrogen permeable film is made of a metal having a hydrogen storage performance, volume expansion occurs at the time of hydrogen storage, but peeling due to this is also suppressed,
The durability of the hydrogen permeable membrane unit is significantly improved.
【００４０】請求項４に係る発明によれば、多孔質支持
体の表層部に研磨を施して研磨片からなる肉薄部分を形
成し、該肉薄部分によつて表面の空孔を大略塞いで平滑
状平面を形成させた後、該多孔質支持体の表面に水素透
過膜を成膜させ、次いで、肉薄部分を除去する。このよ
うに、多孔質支持体の孔を多孔質支持体の肉薄部分によ
つて埋めて平滑状面を形成した後に水素透過膜を成膜さ
せるので、請求項１，２に係る発明と同様の効果を奏す
ることができる。According to the fourth aspect of the present invention, the surface layer of the porous support is polished to form a thin portion made of a polished piece, and the thin portion substantially closes the pores on the surface and is smooth. After forming the flat surface, a hydrogen permeable film is formed on the surface of the porous support, and then the thin portion is removed. As described above, the hydrogen permeable membrane is formed after the pores of the porous support are filled with the thin portions of the porous support to form a smooth surface, and thus the same as in the first and second aspects of the present invention. The effect can be achieved.
【図１】 本発明の第１実施の形態に係る水素透過膜ユ
ニットの概略を示す断面図。FIG. 1 is a sectional view schematically showing a hydrogen permeable membrane unit according to a first embodiment of the present invention.
【図２】 同じく要部を示す拡大図。FIG. 2 is an enlarged view showing a main part of the same.
【図３】 他の構造例に係る水素透過膜ユニットの要部
を示す拡大図。FIG. 3 is an enlarged view showing a main part of a hydrogen permeable membrane unit according to another structural example.
【図４】 本発明の第２実施の形態に係る水素透過膜ユ
ニットの製造過程を示す拡大図。FIG. 4 is an enlarged view showing a manufacturing process of the hydrogen permeable membrane unit according to the second embodiment of the present invention.
【図５】 同じく製造過程を示す拡大図。FIG. 5 is an enlarged view showing the same manufacturing process.
【図６】 同じく製造過程を示す拡大図。FIG. 6 is an enlarged view showing the same manufacturing process.
【図７】 本発明の第２実施の形態に係る水素透過膜ユ
ニットの要部を示す拡大図。FIG. 7 is an enlarged view showing a main part of a hydrogen permeable membrane unit according to a second embodiment of the present invention.
【図８】 本発明の第３実施の形態に係る水素透過膜ユ
ニットの製造過程を示す拡大図。FIG. 8 is an enlarged view showing a process of manufacturing the hydrogen permeable membrane unit according to the third embodiment of the present invention.
【図９】 同じく製造過程を示す拡大図。FIG. 9 is an enlarged view showing the same manufacturing process.
【図１０】 本発明の第３実施の形態に係る水素透過膜
ユニットの要部を示す拡大図。FIG. 10 is an enlarged view showing a main part of a hydrogen permeable membrane unit according to a third embodiment of the present invention.
【図１１】 従来の水素透過膜ユニットを示す断面図。FIG. 11 is a sectional view showing a conventional hydrogen permeable membrane unit.
【図１２】 同じく要部を示す拡大図。FIG. 12 is an enlarged view showing a main part of the same.
【図１３】 同じく要部を示す拡大図。FIG. 13 is an enlarged view showing a main part of the same.
１：水素透過膜ユニット、２：水素透過膜、２ａ：Ｐｄ
又はＰｄ合金（白金族元素又はその合金）、２ｂ：非Ｐ
ｄ合金、２ｃ：Ｐｄ又はＰｄ合金（白金族元素又はその
合金）、３：枠体、４：多孔質支持体、４ａ：多孔体粒
子、４ｂ：凸部、４ｃ：肉薄部分、５，６：接合部、
７：穴埋材。1: hydrogen permeable membrane unit, 2: hydrogen permeable membrane, 2a: Pd
Or Pd alloy (platinum group element or alloy thereof), 2b: non-P
d alloy, 2c: Pd or Pd alloy (platinum group element or alloy thereof), 3: frame, 4: porous support, 4a: porous particle, 4b: convex portion, 4c: thin portion, 5, 6: Joints,
7: Filling material.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 海老沢 孝 神奈川県横浜市金沢区福浦２丁目２−１ 株式会社日本製鋼所内 Ｆターム(参考） 4D006 GA41 MA07 MA08 MA10 MA31 MB03 MC02X MC03 MC04 NA31 NA32 NA33 NA46 NA49 NA50 PA01 PB66 PC69 4G040 FA02 FB09 FC01 FD04 FE01 5H027 AA02 BA16 DD05 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Takashi Ebisawa 2-2-1 Fukuura, Kanazawa-ku, Yokohama-shi, Kanagawa F-term in Japan Steel Works, Ltd. (reference) 4D006 GA41 MA07 MA08 MA10 MA31 MB03 MC02X MC03 MC04 NA31 NA32 NA33 NA46 NA49 NA50 PA01 PB66 PC69 4G040 FA02 FB09 FC01 FD04 FE01 5H027 AA02 BA16 DD05
Claims (5)
水素透過膜（２）を有する水素透過膜ユニットであつ
て、前記水素透過膜（２）が、多孔質支持体（４）に含
有させた穴埋材（７）の上に成膜させた後に該穴埋材
（７）を除去して形成されていることを特徴とする水素
透過膜ユニット。1. A hydrogen permeable membrane unit having a hydrogen permeable membrane (2) bonded to a surface of a porous support (4), wherein the hydrogen permeable membrane (2) is a porous support (4). A hydrogen permeable membrane unit formed by forming a film on the hole filling material (7) contained in the above and removing the hole filling material (7).
水素透過膜（２）を有する水素透過膜ユニットの製造方
法であつて、多孔質支持体（４）の少なくとも表層部に
穴埋材（７）を含有させて表面の空孔を塞いだ後、該多
孔質支持体（４）及び穴埋材（７）の表面に水素透過膜
（２）を成膜させ、次いで、穴埋材（７）を除去するこ
とを特徴とする水素透過膜ユニットの製造方法。2. A method for producing a hydrogen permeable membrane unit having a hydrogen permeable membrane (2) bonded to a surface of a porous support (4), wherein a hole is formed in at least a surface layer of the porous support (4). After filling the pores on the surface with the filling material (7), a hydrogen-permeable membrane (2) is formed on the surfaces of the porous support (4) and the filling material (7). A method for manufacturing a hydrogen permeable membrane unit, comprising removing a filling material (7).
水素透過膜（２）を有する水素透過膜ユニットの製造方
法であつて、多孔質支持体（４）の少なくとも表層部に
穴埋材（７）を含有させて表面の空孔を塞ぐと共に、多
孔質支持体（４）の表面の穴埋材（７）を除去して多孔
体粒子（４ａ）からなる凸部（４ｂ）を形成させた後、
多孔質支持体（４）及び穴埋材（７）の表面に水素透過
膜（２）を成膜させ、次いで、穴埋材（７）を除去する
ことを特徴とする水素透過膜ユニットの製造方法。3. A method for producing a hydrogen permeable membrane unit having a hydrogen permeable membrane (2) bonded to a surface of a porous support (4), wherein a hole is formed in at least a surface layer of the porous support (4). The filling material (7) is contained to close the pores on the surface, and the filling material (7) on the surface of the porous support (4) is removed to form a convex portion (4b) made of porous particles (4a). After forming
Production of a hydrogen permeable membrane unit, characterized in that a hydrogen permeable membrane (2) is formed on the surfaces of the porous support (4) and the hole filling material (7), and then the hole filling material (7) is removed. Method.
水素透過膜（２）を有する水素透過膜ユニットの製造方
法であつて、多孔質支持体（４）の表層部に研磨を施し
て研磨片からなる肉薄部分（４ｃ）を形成し、該肉薄部
分（４ｃ）によつて表面の空孔を大略塞いで平滑状平面
を形成させた後、該多孔質支持体（４）の表面に水素透
過膜（２）を成膜させ、次いで、腐食液に浸して肉薄部
分（４ｃ）を除去することを特徴とする水素透過膜ユニ
ットの製造方法。4. A method for producing a hydrogen permeable membrane unit having a hydrogen permeable membrane (2) bonded to the surface of a porous support (4), wherein the surface layer of the porous support (4) is polished. To form a thin portion (4c) made of a polishing piece, and to form a smooth flat surface by substantially closing the pores on the surface with the thin portion (4c). A method for producing a hydrogen-permeable membrane unit, comprising: forming a hydrogen-permeable membrane (2) on the surface; and immersing the hydrogen-permeable membrane (2) in an etchant to remove the thin portion (4c).
ｂ）の表裏両面を白金族元素又はその合金（２ａ，２
ｃ）によつてコーティングして形成されていることを特
徴とする請求項２，３又は４の水素透過膜ユニットの製
造方法。5. A non-Pd alloy (2) comprising a hydrogen permeable membrane (2).
b) a platinum group element or its alloy (2a, 2
5. The method for producing a hydrogen-permeable membrane unit according to claim 2, wherein the hydrogen-permeable membrane unit is formed by coating according to c).
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007054788A (en) * | 2005-08-26 | 2007-03-08 | Sumitomo Metal Mining Co Ltd | Hydrogen-permeable alloy membrane and its manufacturing method |
| JP2007229616A (en) * | 2006-02-28 | 2007-09-13 | National Institute Of Advanced Industrial & Technology | Hydrogen separation complex and its manufacturing method |
| JP2007307848A (en) * | 2006-05-22 | 2007-11-29 | National Institute For Materials Science | Multilayered thin film and its manufacturing method |
| US7393392B2 (en) | 2004-02-27 | 2008-07-01 | Mikuni Corporation | Hydrogen-permeable membrane and process for production thereof |
| WO2008081855A1 (en) | 2006-12-28 | 2008-07-10 | Mikuni Corporation | Hydrogen permeable film and method for manufacturing the same |
-
2001
- 2001-05-14 JP JP2001143409A patent/JP2002336664A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7393392B2 (en) | 2004-02-27 | 2008-07-01 | Mikuni Corporation | Hydrogen-permeable membrane and process for production thereof |
| JP2007054788A (en) * | 2005-08-26 | 2007-03-08 | Sumitomo Metal Mining Co Ltd | Hydrogen-permeable alloy membrane and its manufacturing method |
| JP2007229616A (en) * | 2006-02-28 | 2007-09-13 | National Institute Of Advanced Industrial & Technology | Hydrogen separation complex and its manufacturing method |
| JP2007307848A (en) * | 2006-05-22 | 2007-11-29 | National Institute For Materials Science | Multilayered thin film and its manufacturing method |
| WO2008081855A1 (en) | 2006-12-28 | 2008-07-10 | Mikuni Corporation | Hydrogen permeable film and method for manufacturing the same |
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