JPH0576737A - Production for hydrogen separation membrane - Google Patents
Production for hydrogen separation membraneInfo
- Publication number
- JPH0576737A JPH0576737A JP24364891A JP24364891A JPH0576737A JP H0576737 A JPH0576737 A JP H0576737A JP 24364891 A JP24364891 A JP 24364891A JP 24364891 A JP24364891 A JP 24364891A JP H0576737 A JPH0576737 A JP H0576737A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- separation membrane
- porous body
- 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.)
- Withdrawn
Links
- 239000001257 hydrogen Substances 0.000 title claims abstract description 38
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 38
- 239000012528 membrane Substances 0.000 title claims abstract description 24
- 238000000926 separation method Methods 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 125000004435 hydrogen atom Chemical class [H]* 0.000 title 1
- 239000002184 metal Substances 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010409 thin film Substances 0.000 claims abstract description 18
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 6
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 5
- 239000000956 alloy Substances 0.000 claims abstract description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011148 porous material Substances 0.000 abstract description 18
- 238000007751 thermal spraying Methods 0.000 abstract description 11
- 238000009423 ventilation Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- 238000013461 design Methods 0.000 abstract description 5
- 238000010030 laminating Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 16
- 239000000843 powder Substances 0.000 description 12
- 239000010408 film Substances 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910010272 inorganic material Inorganic materials 0.000 description 5
- 239000011147 inorganic material Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- LNSPFAOULBTYBI-UHFFFAOYSA-N [O].C#C Chemical group [O].C#C LNSPFAOULBTYBI-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010289 gas flame spraying Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は混合ガス中の水素を分離
するための水素分離膜の製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing a hydrogen separation membrane for separating hydrogen in a mixed gas.
【０００２】[0002]
【従来の技術】省エネルギー型分離技術として、近年、
膜による気体の分離法が注目を集めている。水素含有気
体から水素を分離し、９９．９９％以上の高純度の水素
を得る方法としてＰｄを主体とする膜を使用する方法が
知られている。2. Description of the Related Art Recently, as an energy-saving separation technology,
Membrane separation of gas is drawing attention. As a method for separating hydrogen from a hydrogen-containing gas to obtain high-purity hydrogen of 99.99% or more, a method using a membrane mainly containing Pd is known.
【０００３】従来、水素分離膜はＰｄ又はＰｄを主体と
する合金を伸延し、薄膜とすることによって製造され、
この膜は支持枠で支持して使用されていた。伸延法によ
って得られる膜の厚みの下限には限度があり、又この膜
は支持枠で支持して使用されるため、このような支持方
法に耐えるだけの機械的強度を付与する必要があり、あ
まり薄い膜を使用すると使用中に膜が破損し易い。Conventionally, a hydrogen separation membrane is manufactured by extending Pd or an alloy mainly containing Pd into a thin film,
This membrane was used while being supported by a support frame. There is a limit to the lower limit of the thickness of the film obtained by the distraction method, and since this film is used by being supported by a supporting frame, it is necessary to impart mechanical strength sufficient to withstand such a supporting method. If a thin film is used, the film is likely to break during use.
【０００４】また、セラミックスなど無機質材料からな
る多孔質体の表面にＰｄを含有する薄膜を形成させた水
素分離膜が提案されている。Further, a hydrogen separation membrane has been proposed in which a thin film containing Pd is formed on the surface of a porous body made of an inorganic material such as ceramics.
【０００５】更に、また、セラミックスなど無機質材料
に代わり、０．１〜２０μｍの細孔を有する多孔質金属
体を担体とし、表面にＰｄを含有する薄膜を形成させた
水素分離膜も提案されている。この多孔質金属担体の製
造方法としては、発泡（多孔質）金属をプレス成形し
細孔径を制御したもの。粒径の小さい金属微粉末（５
０μｍ以下）を焼結成形したもの。化学反応により除
去可能な粉末を金属粉末に混合又は溶融した金属に添加
した後、粉末を化学反応により除去し細孔を生成させた
ものなどがある。Further, there has been proposed a hydrogen separation membrane in which a porous metal body having pores of 0.1 to 20 μm is used as a carrier instead of an inorganic material such as ceramics and a thin film containing Pd is formed on the surface. There is. As a method for producing this porous metal carrier, a foamed (porous) metal is press-molded to control the pore size. Fine metal powder with small particle size (5
0 μm or less) sintered and molded. For example, a powder that can be removed by a chemical reaction is added to a metal mixed or melted with a metal powder, and then the powder is removed by a chemical reaction to generate pores.
【０００６】[0006]
【発明が解決しようとする課題】前述した従来の方法に
ついては、各々次のような問題点がある。The above-mentioned conventional methods have the following problems, respectively.
【０００７】（１）Ｐｄを伸延法により薄くする方法は
６０〜１００μｍ程度の比較的厚いものを使用しなくて
はならず、高価なＰｄの使用量が増大し、また水素の透
過速度が小さい。(1) In the method of thinning Pd by the stretching method, a relatively thick Pd of about 60 to 100 μm must be used, the amount of expensive Pd used increases, and the hydrogen permeation rate is low. ..
【０００８】（２）セラミックスなど無機質材料からな
る多孔体担体にＰｄを含有する薄膜を形成させた水素分
離膜は担体が 脆性材料であり機械的強度、振動・衝
撃に弱いため、担体を破損しないように保持することが
困難であり、特別な容器や支持法の設計を要する。
硬いため加工性が悪く、長尺のパイプ状の担体を得るこ
とが難しく設計の自由度も小さい。 溶接ができない
ためシール部の構造が複雑になる。(2) A hydrogen separation membrane, in which a thin film containing Pd is formed on a porous carrier made of an inorganic material such as ceramics, is a brittle material and is not susceptible to mechanical strength, vibration and impact, so that the carrier is not damaged. Are difficult to hold and require special container and support design.
Since it is hard, workability is poor, and it is difficult to obtain a long pipe-shaped carrier, and the degree of freedom in design is small. Since welding is not possible, the structure of the seal part becomes complicated.
【０００９】（３）セラミックスなど無機質材料に代
え、多孔質金属の担体にＰｄを含有する薄膜を形成させ
てなる水素分離膜は提案されている多孔質金属担体の製
造方法としては、 発泡（多孔質）金属をプレス成形
し細孔径を制御したもの。 粒径の小さい金属微粉末
（５０μｍ以下）を焼結成形したもの。 化学反応に
より除去可能な粉末を金属粉末に混合または溶融した金
属に添加した後、粉末を化学反応により除去し細孔を生
成させたものなど提案されているが、何れも加工性が悪
く薄肉で長尺のパイプを製造することが難しく、製造で
きるとしても耐圧強度を大きくするためには厚肉が必要
で通気抵抗が大きくなり、水素分離膜の担体として適さ
ない。(3) A hydrogen separation membrane in which a thin film containing Pd is formed on a porous metal carrier instead of an inorganic material such as ceramics is proposed as a method for producing a porous metal carrier. Material) A metal that is press-molded to control the pore size. Sintered compact metal fine powder (50 μm or less) with small particle size. It has been proposed that powder that can be removed by a chemical reaction is mixed with metal powder or added to a molten metal, and then the powder is removed by a chemical reaction to create pores, but both are poor in processability and thin. It is difficult to manufacture a long pipe, and even if it can be manufactured, a thick wall is required to increase the pressure resistance and the ventilation resistance becomes large, which is not suitable as a carrier for a hydrogen separation membrane.
【００１０】本発明は上記技術水準に鑑み、従来法にお
けるような不具合のない水素分離膜の製造方法を提供し
ようとするものである。In view of the above-mentioned state of the art, the present invention is to provide a method for producing a hydrogen separation membrane which does not have the problems of the conventional method.
【００１１】[0011]
【課題を解決するための手段】本発明は金属多孔体表面
に金属あるいは金属酸化物を溶射後、水素雰囲気中で加
熱処理を行い、次いで該金属多孔体の溶射側の表面にＰ
ｄまたはＰｄを含有する合金の薄膜を形成させることを
特徴とする水素分離膜の製造方法である。According to the present invention, after spraying a metal or a metal oxide on the surface of a metal porous body, a heat treatment is performed in a hydrogen atmosphere, and then the surface of the metal porous body on the sprayed side is subjected to P treatment.
A method for producing a hydrogen separation membrane, which comprises forming a thin film of an alloy containing d or Pd.
【００１２】本発明に使用される金属多孔体としてはＳ
ＵＳ３０４Ｌ，ＳＵＳ３１６Ｌ，ハステロイＣ等の材質
のものが好ましく、一般に多孔度は１０〜４０％程度の
ものが使用される。金属多孔体として金網を使用する場
合には、金網の線径と目開きから多孔度（開口率）は決
まり、理論的にはかなり多孔度が大となるが一般的に市
販の金網の多孔度は上記範囲になる。The metal porous body used in the present invention is S
Materials such as US304L, SUS316L, and Hastelloy C are preferable, and those having a porosity of about 10 to 40% are generally used. When a wire mesh is used as the metal porous body, the porosity (aperture ratio) is determined from the wire diameter and the opening of the wire mesh, and theoretically the porosity is considerably large, but generally the porosity of commercially available wire mesh. Is in the above range.
【００１３】溶射金属または金属酸化物としてはＮｉ
Ｏ，Ｆｅ2 Ｏ3 ，ＴｉＯ2 ，Ｃｒ2 Ｏ 3 ，ＣｏＯおよび
Ｎｉなどが使用される。Ni as the sprayed metal or metal oxide
O, Fe2O3, TiO2, Cr2O 3, CoO and
Ni or the like is used.
【００１４】[0014]
【作用】本発明は上記従来技術の問題点の Ｐｄを伸
延法により薄くする方法の高価なＰｄの使用量が多く、
また水素の透過速度が小さいこと、 セラミックスな
ど無機質材料からなる多孔体担体にＰｄを含有する薄膜
を形成させる方法の強度及びシール等の問題点を解決す
るための手段及び作用を一例をあげて説明する。According to the present invention, a large amount of expensive Pd is used in the method of thinning Pd by the distraction method, which is a problem of the above-mentioned prior art.
Also, the means and action for solving problems such as strength and sealing in the method of forming a thin film containing Pd on a porous carrier made of an inorganic material such as ceramics will be described by way of example with a low hydrogen permeation rate. To do.
【００１５】耐圧強度を保持するためには５０μｍ以上
の細孔を有する複数枚の金網積層焼結体を製作する。必
要な強度・寸法に応じて金網の積層状態を変えた金属多
孔体が製作できる。この金網積層焼結体を必要な形状
（長尺のパイプ形状等）に加工する。In order to maintain the pressure resistance, a plurality of wire mesh laminated sintered bodies having pores of 50 μm or more are manufactured. It is possible to manufacture a metal porous body in which the laminated state of the wire mesh is changed according to the required strength and size. This wire mesh laminated sintered body is processed into a required shape (long pipe shape or the like).
【００１６】その後、金属或いは金属酸化物を大気中に
て溶射する。この溶射皮膜が酸化物を多く含んだものと
なる条件にて溶射する。また、この溶射により金網積層
焼結体の表面が完全に覆われる必要はなく、１０μｍ以
下の細孔が数多く存在する多孔質の方が望ましい。After that, a metal or a metal oxide is sprayed in the atmosphere. Thermal spraying is performed under the condition that the thermal spray coating contains a large amount of oxide. Further, it is not necessary that the surface of the wire mesh laminated sintered body be completely covered by this thermal spraying, and a porous material having a large number of pores of 10 μm or less is preferable.
【００１７】溶射後、水素雰囲気中で加熱して溶射皮膜
中の酸化物を還元する。その結果、溶射皮膜には微小な
細孔が数多く発生する。After thermal spraying, heating is performed in a hydrogen atmosphere to reduce oxides in the thermal spray coating. As a result, many fine pores are generated in the thermal spray coating.
【００１８】上記より製作された金属多孔体の表面は
０．１〜１０μｍと細孔が小さいため３０μｍ以下のＰ
ｄを含有する薄膜を形成させることが容易で、かつ、溶
射皮膜の厚さが０．０５〜０．１０ｍｍの薄膜のため通
気抵抗を大きくしない。その結果、通気抵抗が小さく高
い強度を有すると共に長尺のパイプのように任意の形状
に加工された担体にＰｄを含有する薄膜を薄く形成され
た水素分離膜が製作でき、さらに溶接が可能となり、モ
ジュール化が容易となる。Since the surface of the metal porous body produced as described above has small pores of 0.1 to 10 μm, P of 30 μm or less is obtained.
It is easy to form a thin film containing d, and since the thickness of the sprayed coating is 0.05 to 0.10 mm, the ventilation resistance is not increased. As a result, it is possible to manufacture a hydrogen separation membrane that has a small air resistance and high strength, and a thin Pd-containing thin film formed on a carrier that has been processed into an arbitrary shape such as a long pipe, and can be welded. , Modularization becomes easy.
【００１９】金属多孔体の溶射側表面に膜厚が３０μｍ
以下のＰｄを含有する薄膜を形成させる方法としては、
めっきなどの湿式のコーティング法、 真空蒸着
法、イオンプレーティング、気相反応法（ＣＶＤ）など
のドライコーティング法がある。A film thickness of 30 μm is formed on the surface of the metal porous body on the thermal spraying side.
The following method for forming a thin film containing Pd includes:
There are wet coating methods such as plating, vacuum deposition methods, ion plating, and dry coating methods such as vapor phase reaction (CVD).
【００２０】[0020]
【実施例】本発明の金属多孔体パイプにＰｄを含有する
薄膜を形成させたものの断面構造の模式図を図１に示
す。図１において、１はＰｄを含有する薄膜、２は溶射
後水素還元した薄膜、３は複数枚の金網の積層焼結体を
示す。EXAMPLE FIG. 1 shows a schematic view of a cross-sectional structure of a metal porous pipe of the present invention on which a thin film containing Pd is formed. In FIG. 1, 1 is a thin film containing Pd, 2 is a thin film obtained by hydrogen reduction after thermal spraying, and 3 is a laminated sintered body of a plurality of wire nets.
【００２１】最表層と２層目が線径３８μｍで目開き５
３μｍの金網（２８０メッシュ）で、３層目が線径１０
５μｍで目開き１５０μｍ（１００メッシュ）、４層目
が線径２３０μｍで目開き３００μｍ（４８メッシュ）
の金網（材質何れもＳＵＳ３１６）を１３８０℃×３時
間の条件で積層焼結した金網積層焼結体を製作した。こ
の金網積層焼結体の全厚みは約０．６ｍｍであり、通気
抵抗は表層に１０μｍ程度の細孔を有する皮膜が存在す
る場合には無視できるほど非常に小さい。The outermost layer and the second layer have a wire diameter of 38 μm and an opening of 5
Wire mesh of 3 μm (280 mesh)
5 μm opening 150 μm (100 mesh), 4th layer wire diameter 230 μm opening 300 μm (48 mesh)
A wire mesh laminated sintered body was manufactured by laminating and sintering the wire mesh (all materials were SUS316) at 1380 ° C. for 3 hours. The total thickness of this wire mesh laminated sintered body is about 0.6 mm, and the ventilation resistance is so small that it can be ignored when a film having pores of about 10 μm is present in the surface layer.
【００２２】上記の金網積層焼結体を巻き加工→溶接し
て２０φ×３００Ｌのパイプを製作し、該パイプの外表
面に酸素−アセチレンによるガス炎溶射にてＮｉＯを約
１００μｍ溶射し、その後、所定の条件（４００℃水素
雰囲気中）で還元処理を実施した。このようにして得ら
れた金属多孔体パイプの表面細孔径は０．１〜１０μｍ
で平均細孔径は３μｍ、開口率は約３０％であった。The above wire mesh laminated sintered body is rolled and welded to produce a 20φ × 300 L pipe, and NiO is sprayed on the outer surface of the pipe by gas flame spraying with oxygen-acetylene to about 100 μm. The reduction treatment was performed under predetermined conditions (400 ° C. in a hydrogen atmosphere). The surface pore diameter of the porous metal pipe thus obtained is 0.1 to 10 μm.
The average pore size was 3 μm, and the aperture ratio was about 30%.
【００２３】本発明における金属多孔体パイプの溶射後
及び還元処理後の通気抵抗並びに従来の金属粉末焼結法
により製作した購入パイプ（１７．３φ×１５０Ｌ×
２．０ｔ、細孔径は５μｍ、開孔率３０％）の通気抵抗
測定結果を表１に示す。Ventilation resistance of the porous metal pipe of the present invention after thermal spraying and reduction treatment and a purchased pipe (17.3φ × 150L ×) manufactured by the conventional metal powder sintering method.
Table 1 shows the results of measurement of the ventilation resistance of 2.0 t, the pore diameter of 5 μm, and the open area ratio of 30%).
【００２４】本発明における金属多孔体パイプ及び購入
品の金属粉末焼結体パイプの外表面に同一条件の無電解
めっき（Ｐｄの化合物と還元剤を含有する液に浸漬）に
てＰｄを１０μｍめっきした。各々のパイプにつき、Ｈ
2 混合ガスの圧力を３ｋｇ／ｃｍ2 Ｇ、流量を２０Ｎｌ
／ｍｉｎで、５００℃で実施した水素透過試験結果を表
２に示す。Pd is plated to a thickness of 10 μm on the outer surfaces of the metal porous pipe and the purchased metal powder sintered pipe of the present invention by electroless plating under the same conditions (immersing in a liquid containing a Pd compound and a reducing agent). did. H for each pipe
2 Mixed gas pressure 3kg / cm 2 G, flow rate 20Nl
Table 2 shows the results of the hydrogen permeation test performed at 500 ° C./min.
【００２５】表１に示すように、本発明における金属多
孔体パイプは購入品の金属粉末焼結体パイプに対し、通
気抵抗を上昇させる細孔径の小さい多孔質金属薄膜の厚
みが薄いため、通気抵抗が約１／３０と小さい。As shown in Table 1, since the porous metal pipe of the present invention has a small thickness of the porous metal thin film having a small pore diameter for increasing the ventilation resistance as compared with the purchased metal powder sintered pipe, the ventilation is improved. The resistance is as small as about 1/30.
【００２６】また、表２に示すように、本発明の金属多
孔体パイプにＰｄめっきしたものの水素透過速度は、３
３ｃｍ3 ／ｃｍ2 ・ｍｉｎと従来のＰｄ膜の方法の約８
倍と大きく、購入品の金属粉末焼結体パイプにＰｄめっ
きしたものの約１．８倍である。Also, as shown in Table 2, the hydrogen permeation rate of the Pd-plated metal porous pipe of the present invention is 3
3 cm 3 / cm 2 · min, which is about 8 of the conventional Pd film method
It is twice as large, which is about 1.8 times that of the purchased metal powder sintered pipe that is Pd-plated.
【表１】 [Table 1]
【表２】 [Table 2]
【００２７】なお、本実施例は酸素−アセチレンによる
ガス炎溶射によるＮｉＯの溶射の例を述べたが、酸化物
としてはＦｅ2 Ｏ3 ，ＴｉＯ2 ，Ｃｒ2 Ｏ3 ，ＣｏＯな
どの還元性のあるものは有効であり、溶射としては大気
プラズマ溶射など他の方法でもよい。In this embodiment, an example of thermal spraying of NiO by gas flame spraying with oxygen-acetylene was described, but as the oxide, reducing agents such as Fe 2 O 3 , TiO 2 , Cr 2 O 3 and CoO can be used. Some are effective, and other methods such as atmospheric plasma spraying may be used as the spraying.
【００２８】また、酸化物でなくＮｉなどの金属でも大
気中で溶射することにより、ポーラスで酸化物を多く含
んだ溶射皮膜とすることにより、酸化物と同様の効果が
得られる。Further, by spraying a metal such as Ni instead of an oxide in the atmosphere, a sprayed coating containing a large amount of oxide is porous, and the same effect as the oxide can be obtained.
【００２９】[0029]
【発明の効果】（１）本発明方法においては、強度保持
のための任意枚数の金網積層焼結体に薄く溶射した金属
多孔体をきざ基材としているため、表面細孔径が小さ
く、しかも通気抵抗が小さくでき、水素分離膜の基材と
して適しており、またパイプ曲げ加工や溶接が可能で耐
圧強度の大きい長尺の水素分離膜パイプを製作すること
が可能である。このことにより、設計の自由度が大き
く、大型化やモジュール化が容易となる。EFFECTS OF THE INVENTION (1) In the method of the present invention, since the metal porous body thinly sprayed on an arbitrary number of wire mesh laminated sintered bodies for maintaining strength is used as the base material, the surface pore diameter is small and the ventilation It has a low resistance and is suitable as a base material for hydrogen separation membranes. Moreover, it is possible to manufacture a long hydrogen separation membrane pipe that is bendable and weldable and has high pressure resistance. As a result, the degree of freedom in design is great, and it becomes easy to increase the size and modularization.
【００３０】（２）表面細孔が小さいため薄いＰｄまた
はＰｄ合金膜を形成でき、水素透過量の大きい水素分離
膜が製作でき、かつ高価なＰｄの使用量が少なくてすむ
という利点がある。(2) Since the surface pores are small, a thin Pd or Pd alloy membrane can be formed, a hydrogen separation membrane having a large hydrogen permeation amount can be manufactured, and the amount of expensive Pd used is small.
【図１】本発明方法で得られた水素分離膜の一例の断面
模式図FIG. 1 is a schematic sectional view of an example of a hydrogen separation membrane obtained by the method of the present invention.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 石橋 保博 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 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Yasuhiro Ishibashi 4-6-22 Kannon Shinmachi, Nishi-ku, Hiroshima City Mitsubishi Heavy Industries Ltd. Hiroshima Research Laboratory
Claims (1)
物を溶射後、水素雰囲気中で加熱処理を行い、次いで該
金属多孔体の溶射側の表面にＰｄまたはＰｄを含有する
合金の薄膜を形成させることを特徴とする水素分離膜の
製造方法。1. A metal or metal oxide is sprayed on the surface of a porous metal body, and then heat treatment is carried out in a hydrogen atmosphere, and then a thin film of Pd or an alloy containing Pd is formed on the surface of the sprayed side of the porous metal body. A method for producing a hydrogen separation membrane, comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24364891A JPH0576737A (en) | 1991-09-24 | 1991-09-24 | Production for hydrogen separation membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24364891A JPH0576737A (en) | 1991-09-24 | 1991-09-24 | Production for hydrogen separation membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0576737A true JPH0576737A (en) | 1993-03-30 |
Family
ID=17106946
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24364891A Withdrawn JPH0576737A (en) | 1991-09-24 | 1991-09-24 | Production for hydrogen separation membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0576737A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1362630A1 (en) * | 2002-05-17 | 2003-11-19 | W.C. Heraeus GmbH & Co. KG | Composite membrane and method for its production |
| JP2008246430A (en) * | 2007-03-30 | 2008-10-16 | Nippon Seisen Co Ltd | Membrane support for hydrogen separation and module for hydrogen separation using this support |
-
1991
- 1991-09-24 JP JP24364891A patent/JPH0576737A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1362630A1 (en) * | 2002-05-17 | 2003-11-19 | W.C. Heraeus GmbH & Co. KG | Composite membrane and method for its production |
| US6761755B2 (en) | 2002-05-17 | 2004-07-13 | W. C. Heraeus Gmbh & Co. Kg | Composite membrane and production method therefor |
| JP2008246430A (en) * | 2007-03-30 | 2008-10-16 | Nippon Seisen Co Ltd | Membrane support for hydrogen separation and module for hydrogen separation using this support |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Nam et al. | Hydrogen separation by Pd alloy composite membranes: introduction of diffusion barrier | |
| US7125440B2 (en) | Composite structure for high efficiency hydrogen separation and its associated methods of manufacture and use | |
| KR20090087869A (en) | Sintered Bonded Porous Metal Coating | |
| JPH11276866A (en) | Hydrogen permeable membrane and method for producing the same | |
| US9199204B2 (en) | Hydrogen-separation-membrane protection layer and a coating method therefor | |
| US20020028345A1 (en) | Process for preparing a composite metal membrane, the composite metal membrane prepared therewith and its use | |
| JPH04346824A (en) | Hydrogen separating membrane | |
| JP2002355537A (en) | Hydrogen permeable membrane and method for producing the same | |
| CA3106485A1 (en) | Method for producing an open-pored metal body having an oxide layer and metal body produced by said method | |
| JP3117276B2 (en) | Hydrogen separation membrane | |
| JPH0585702A (en) | Production of hydrogen separation membrane | |
| MX2008006329A (en) | Hydrogen transport membrane fabrication method. | |
| US4781734A (en) | Non-porous hydrogen diffusion membrane and utilization thereof | |
| JPH0576737A (en) | Production for hydrogen separation membrane | |
| JPH05137979A (en) | Production of hydrogen separating membrane | |
| JP3645088B2 (en) | Hydrogen permeable membrane and method for producing the same | |
| CN206214907U (en) | Filtering material and the filter element using the filtering material | |
| TW201325696A (en) | Methods of fabricating porous media and inorganic selective film | |
| JPH0691144A (en) | Production of hydrogen separating membrane | |
| JPH05123548A (en) | Production of hydrogen separation membrane | |
| JPH01131004A (en) | Production of hydrogen-separating membrane | |
| JP2004122006A (en) | Hydrogen separation membrane, method for producing the same, and method for separating hydrogen | |
| WO2005075060A1 (en) | Composite structure for high efficiency hydrogen separation and its associated methods of manufacture and use | |
| JP3174668B2 (en) | Hydrogen separation membrane | |
| US7749305B1 (en) | Composite structure for high efficiency hydrogen separation containing preformed nano-particles in a bonded layer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 19981203 |