JPH01131004A - Production of hydrogen-separating membrane - Google Patents
Production of hydrogen-separating membraneInfo
- Publication number
- JPH01131004A JPH01131004A JP28880787A JP28880787A JPH01131004A JP H01131004 A JPH01131004 A JP H01131004A JP 28880787 A JP28880787 A JP 28880787A JP 28880787 A JP28880787 A JP 28880787A JP H01131004 A JPH01131004 A JP H01131004A
- Authority
- JP
- Japan
- Prior art keywords
- filler
- hydrogen
- substrate
- alloy layer
- void
- 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
- 239000012528 membrane Substances 0.000 title abstract description 10
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 239000000945 filler Substances 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 238000003860 storage Methods 0.000 claims description 12
- 239000010953 base metal Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 abstract description 12
- 239000000956 alloy Substances 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 abstract description 4
- 229920006380 polyphenylene oxide Polymers 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000010935 stainless steel Substances 0.000 abstract description 2
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 2
- 239000011800 void material Substances 0.000 abstract 3
- 229910002335 LaNi5 Inorganic materials 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000010408 film Substances 0.000 description 4
- 229910001252 Pd alloy Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- -1 is For example Substances 0.000 description 1
- DOARWPHSJVUWFT-UHFFFAOYSA-N lanthanum nickel Chemical compound [Ni].[La] DOARWPHSJVUWFT-UHFFFAOYSA-N 0.000 description 1
- ATTFYOXEMHAYAX-UHFFFAOYSA-N magnesium nickel Chemical compound [Mg].[Ni] ATTFYOXEMHAYAX-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
Description
【発明の詳細な説明】
Ｕノ 産業上の利用分野
本発明は、高純度の水素ｅｌｎｔ製する装置等で用いら
れる水素分離膜の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing a hydrogen separation membrane used in an apparatus for producing high-purity hydrogen.
（Ｉ従来の技術
半導体の還元工程等で大量に使用される高純度水素は、
例えば銀・パラジクム合金膜透過法？利用した水素精製
装置によって製造されている。(I) Conventional technology: High-purity hydrogen, which is used in large quantities in the reduction process of semiconductors, is
For example, silver/palladium alloy membrane permeation method? It is produced using hydrogen purification equipment.
しかし、この装置は銀・パラジウム合金が高価であるこ
と、精製時に４００℃以上の高温が必要であることと云
う欠点がある。However, this device has disadvantages in that the silver-palladium alloy is expensive and that high temperatures of 400° C. or higher are required during purification.
そこで、銀・パラジウム合金に代る安価な水素吸蔵合金
を用いることが考えらｎ１更に水素精製のプロセス速度
を上げるために、膜厚が薄い水素分離膜が要望された。Therefore, it was considered to use an inexpensive hydrogen storage alloy instead of the silver-palladium alloy, and in order to further increase the process speed of hydrogen purification, a hydrogen separation membrane with a thin film thickness was desired.
とこ）が、膜厚に０．１〜５μｍ程度とすると、機械的
強度を呆持するために相持体が必要と成る。However, if the film thickness is approximately 0.1 to 5 μm, a supporting body is required to maintain mechanical strength.
現状では特開昭６２−１９１４０２号公報で示されるよ
うに、多孔質で通気性を有する例えば焼結金属基板に、
スパッタ法或いは蒸着法で約３０μｍ程度の厚さで水素
吸蔵台金層を形成していた。Currently, as shown in Japanese Unexamined Patent Publication No. 191402/1983, for example, a porous and breathable sintered metal substrate,
The hydrogen storage base metal layer was formed to a thickness of about 30 μm by sputtering or vapor deposition.
０９ 発明が解決しようとする問題点しかし、このも
のは、焼結金属基板の表面に細孔があるので、極めて平
坦性が悪く、この表面に形成さｎた水素吸蔵合金層も膜
厚が不均一となり、ピンホールが発生しやすい。09 Problems to be Solved by the Invention However, in this case, since the surface of the sintered metal substrate has pores, the flatness is extremely poor, and the hydrogen storage alloy layer formed on this surface also has an irregular film thickness. It becomes uniform and pinholes are likely to occur.
本発明は、ピンホールの発生？抑えて水素分離膜の性能
全向上せんとするものである。Does the present invention cause pinholes? The aim is to improve the performance of hydrogen separation membranes while minimizing the amount of hydrogen separation.
に）問題点？解決するための手段
本発明による解決手段は、多孔質で通気性？有する基板
の空孔部に充填剤全充填して該空孔部全閉塞し、次いで
空孔部を含む基板の表面全切削し、研磨して平坦面に形
成し、次いでこの平坦面上に水素吸蔵合金層を均一に形
成し、この後に上記充填剤を空孔部から溶出除去した構
成である。) Problem? Solution The solution according to the invention is porous and breathable? The pores of the substrate are completely filled with filler to completely block the pores, the entire surface of the substrate including the pores is cut and polished to form a flat surface, and hydrogen is then applied on the flat surface. The structure is such that a storage alloy layer is uniformly formed, and then the filler is eluted and removed from the pores.
（ホ）作用
即ち、基板表面を充填剤毎切削して研磨すると、基板及
び充填剤により平坦面が形成され、この平坦面上に水素
吸蔵合金層を均一に形成する。(e) Operation: When the substrate surface is cut and polished along with the filler, a flat surface is formed by the substrate and the filler, and a hydrogen storage alloy layer is uniformly formed on this flat surface.
そして、充填剤のみを適当な溶剤等で除去すると、基板
表面上に平坦に水素吸蔵合金属が残シ、膜厚も均一とな
るので、薄くてもピンホールは発生しにくい。When only the filler is removed using a suitable solvent, the hydrogen-absorbing metal alloy remains flat on the substrate surface and the film thickness is uniform, so pinholes are less likely to occur even if the film is thin.
（へ）実施例
第１図に基づいて説明すると、例えば最大空孔直径１．
ａｍで通気性を有するステンレス焼結体から成る基板１
に、耐熱性高分子材料の一種であるポリフェニレンオキ
シド全充填剤２として加える。即ち、このポリフェニレ
ンオキシドの飽和トルエン溶液中に基板ｌｔ−浸漬し、
全ての空孔部全閉塞すると共に全表面に被覆する。(f) Example To explain based on FIG. 1, for example, the maximum pore diameter is 1.
Substrate 1 made of a stainless steel sintered body having air permeability at am
Polyphenylene oxide, which is a type of heat-resistant polymeric material, is added as a total filler 2. That is, the substrate is lt-immersed in a saturated toluene solution of this polyphenylene oxide,
All pores are completely closed and the entire surface is coated.
そして、取シ出して乾燥し、この後に基板ｌの表面を充
填剤２と共に切削し、更に研磨して充填剤２が一部を構
成する平坦面３を形成する。Then, it is taken out and dried, and then the surface of the substrate 1 is cut together with the filler 2 and further polished to form a flat surface 3 of which the filler 2 forms a part.
次層で、平坦面３上に水素吸蔵合金層４としてランタン
・ニッケル合金（ＬａＮ ｉ ｓ、）２１μｍの厚さで
スパッタ法によって均一に形成する。As the next layer, a hydrogen storage alloy layer 4 of lanthanum-nickel alloy (LaNiS) is uniformly formed on the flat surface 3 to a thickness of 21 μm by sputtering.
次に、水素吸蔵台金層４が形成さ扛た基板１全、約６０
℃に刀ｎ熱さｎたトルエン、クロロホルム、ニトロベン
ゼン等の溶剤中で、超音波洗浄し、基板１の空孔部に在
る充填剤２（ポリフェニレンオキシド）を溶出して除去
する。Next, about 60% of the substrate 1 on which the hydrogen storage base metal layer 4 was formed was removed.
The filler 2 (polyphenylene oxide) present in the pores of the substrate 1 is eluted and removed by ultrasonic cleaning in a solvent such as toluene, chloroform, or nitrobenzene heated to a temperature of 0.degree.
最後に基板ｌ全体をアセトン洗浄し、この後に真空乾燥
する。Finally, the entire substrate 1 is cleaned with acetone, and then vacuum dried.
かくして、得らｆした水素分離膜５は、気密度試験の結
果、ピンホールが存在しないことケ確認さｎた。As a result of the airtightness test, it was confirmed that the hydrogen separation membrane 5 thus obtained had no pinholes.
基板ｌは、通常の金属焼結体、ガラス、セラミック等も
オリ用できる。The substrate 1 may be a normal metal sintered body, glass, ceramic, or the like.
水素吸蔵合金層４は、希土類・ニッケル基台金、チタニ
クム基台金、マグネシクム・ニッケル基台金全採用す・
ることもでき、その形成方法は、スパッタ法の他に、イ
オンブレーティング法、蒸着法等も利用できる。The hydrogen storage alloy layer 4 uses all rare earth/nickel based metals, titanium based metals, and magnesium nickel based metals.
In addition to the sputtering method, ion blating method, vapor deposition method, etc. can also be used for the formation method.
充填剤２は、耐熱性高分子等の樹脂で良く、その除去用
溶剤は採用樹脂に応じて選択する。The filler 2 may be a resin such as a heat-resistant polymer, and the solvent for its removal is selected depending on the resin used.
因みに、水素分離膜５全不発明方法によって得た場合と
従来方法によって得た場合の比較を次表で示す。Incidentally, the following table shows a comparison between the hydrogen separation membrane 5 obtained by the completely uninvented method and the case obtained by the conventional method.
（トノ発明の効果
不発明に依ｎば、基板に多孔質で通気性？有するもの全
周いた場合でも水素吸蔵合金層勿平坦面上に均一に形成
できると共に、基板の通気性を保持できる。このために
形属さｎた水素吸蔵合金１−でのピンホールの発生を抑
制、防止して、極めて高性能の水部分１１１Ｊｉｌ得る
ことができるものである。(Advantages of the Invention According to the invention, even if the substrate is porous and has air permeability all around it, the hydrogen storage alloy layer can be uniformly formed on a flat surface, and the air permeability of the substrate can be maintained. For this reason, it is possible to suppress and prevent the formation of pinholes in the shaped hydrogen storage alloy 1-, and to obtain an extremely high-performance water portion 111Jil.
第１１９）（ロ）し９に）（ホ）は本発明方法を順に示
す断面図である。
１・・・基板、２・・・充填剤、３・・・平坦面、４・
・・水素吸蔵合金層、５・・・水素分離膜。119)(B) to 9)(E) are sectional views sequentially showing the method of the present invention. DESCRIPTION OF SYMBOLS 1... Substrate, 2... Filler, 3... Flat surface, 4...
...Hydrogen storage alloy layer, 5...Hydrogen separation membrane.
Claims (1)
充填して該空孔部を閉塞し、次いで空孔部を含む基板の
表面を切削し、研磨して平坦面に形成し、次いでこの平
坦面上に水素吸蔵台金層を均一に形成し、この後に上記
充填剤を空孔部から溶出除去して成る水素分離膜の製造
方法。(1) Fill the pores of a porous and breathable substrate with a filler to close the pores, and then cut and polish the surface of the substrate including the pores to form a flat surface. Then, a hydrogen storage base metal layer is uniformly formed on the flat surface, and the filler is then eluted and removed from the pores.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28880787A JPH01131004A (en) | 1987-11-16 | 1987-11-16 | Production of hydrogen-separating membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28880787A JPH01131004A (en) | 1987-11-16 | 1987-11-16 | Production of hydrogen-separating membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01131004A true JPH01131004A (en) | 1989-05-23 |
Family
ID=17734985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28880787A Pending JPH01131004A (en) | 1987-11-16 | 1987-11-16 | Production of hydrogen-separating membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01131004A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2253173A (en) * | 1991-03-01 | 1992-09-02 | Aerospace Systems & Tech | Process for the mechanical treatment of porous sheet materials |
| US5827569A (en) * | 1994-07-29 | 1998-10-27 | Akiyama; Shigeo | Hydrogen separation membrane and process for producing the same |
| WO2004011130A1 (en) * | 2002-07-25 | 2004-02-05 | Dai Nippon Insatsu Kabushiki Kaisha | Thin film supporting substrate used in filter for hydrogen production and method for manufacturing filter for hydrogen production |
| JP2004057993A (en) * | 2002-07-31 | 2004-02-26 | Dainippon Printing Co Ltd | Method of manufacturing hydrogen producing filter |
| JP2007517655A (en) * | 2004-01-09 | 2007-07-05 | ビーピー ピー・エル・シー・ | Metal palladium composite membrane or alloy palladium composite membrane and method for producing the same |
| JP2007229616A (en) * | 2006-02-28 | 2007-09-13 | National Institute Of Advanced Industrial & Technology | Hydrogen separation complex and its manufacturing method |
| JP2008246317A (en) * | 2007-03-29 | 2008-10-16 | Ngk Spark Plug Co Ltd | Hydrogen separator and fuel cell |
| JP2009125632A (en) * | 2007-11-21 | 2009-06-11 | Ngk Insulators Ltd | Gas separation material and its manufacturing method |
-
1987
- 1987-11-16 JP JP28880787A patent/JPH01131004A/en active Pending
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2253173A (en) * | 1991-03-01 | 1992-09-02 | Aerospace Systems & Tech | Process for the mechanical treatment of porous sheet materials |
| US5333415A (en) * | 1991-03-01 | 1994-08-02 | Aerospace Systems & Technologies Ltd. | Process for sealing a perforated web material |
| US5827569A (en) * | 1994-07-29 | 1998-10-27 | Akiyama; Shigeo | Hydrogen separation membrane and process for producing the same |
| EP1946826A1 (en) * | 2002-07-25 | 2008-07-23 | Dai Nippon Insatsu Kabushiki Kaisha | Production method of hydrogen production filter |
| WO2004011130A1 (en) * | 2002-07-25 | 2004-02-05 | Dai Nippon Insatsu Kabushiki Kaisha | Thin film supporting substrate used in filter for hydrogen production and method for manufacturing filter for hydrogen production |
| US7112287B2 (en) | 2002-07-25 | 2006-09-26 | Dai Nippon Insatsu Kabushiki Kaisha | Thin film supporting substrate for used in filter for hydrogen production filter and method for manufacturing filter for hydrogen production |
| US8043519B2 (en) | 2002-07-25 | 2011-10-25 | Dai Nippon Insatsu Kabushiki Kaisha | Thin film support substrate for use in hydrogen production filter and production method of hydrogen production filter |
| US7241396B2 (en) | 2002-07-25 | 2007-07-10 | Dai Nippon Insatsu Kabushiki Kaisha | Thin film support substrate for use in hydrogen production filter and production method of hydrogen production filter |
| US7803263B2 (en) | 2002-07-25 | 2010-09-28 | Dai Nippon Insatsu Kabushiki Kaisha | Thin film support substrate for use in hydrogen production filter and production method of hydrogen production filter |
| US7399423B2 (en) | 2002-07-25 | 2008-07-15 | Dai Nippon Insatsu Kabushiki Kaisha | Thin film support substrate for use in hydrogen production filter and production method of hydrogen production filter |
| US7744990B2 (en) | 2002-07-25 | 2010-06-29 | Dai Nippon Insatsu Kabushiki Kaisha | Thin film support substrate for use in hydrogen production filter and production method of hydrogen production filter |
| US8562847B2 (en) | 2002-07-25 | 2013-10-22 | Dai Nippon Insatsu Kabushiki Kaisha | Thin film support substrate for use in hydrogen production filter and production method of hydrogen production filter |
| US8163157B2 (en) | 2002-07-25 | 2012-04-24 | Dai Nippon Insatsu Kabushiki Kaisha | Method of producing a hydrogen production filter |
| JP2004057993A (en) * | 2002-07-31 | 2004-02-26 | Dainippon Printing Co Ltd | Method of manufacturing hydrogen producing filter |
| JP4681201B2 (en) * | 2002-07-31 | 2011-05-11 | 大日本印刷株式会社 | HYDROGEN PRODUCTION FILTER AND ITS MANUFACTURING METHOD |
| US8052775B2 (en) | 2004-01-09 | 2011-11-08 | Bp P.L.C. | Process for the preparation of a two-layer metal palladium or palladium alloy composite membrane |
| JP2007517655A (en) * | 2004-01-09 | 2007-07-05 | ビーピー ピー・エル・シー・ | Metal palladium composite membrane or alloy palladium composite membrane and method for producing the same |
| JP2007229616A (en) * | 2006-02-28 | 2007-09-13 | National Institute Of Advanced Industrial & Technology | Hydrogen separation complex and its manufacturing method |
| JP2008246317A (en) * | 2007-03-29 | 2008-10-16 | Ngk Spark Plug Co Ltd | Hydrogen separator and fuel cell |
| JP2009125632A (en) * | 2007-11-21 | 2009-06-11 | Ngk Insulators Ltd | Gas separation material and its manufacturing method |
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