JPH0579367B2 - - Google Patents
Info
- Publication number
- JPH0579367B2 JPH0579367B2 JP8469389A JP8469389A JPH0579367B2 JP H0579367 B2 JPH0579367 B2 JP H0579367B2 JP 8469389 A JP8469389 A JP 8469389A JP 8469389 A JP8469389 A JP 8469389A JP H0579367 B2 JPH0579367 B2 JP H0579367B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- alloy
- palladium
- atomic
- membrane
- 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.)
- Expired - Lifetime
Links
- 239000001257 hydrogen Substances 0.000 claims description 56
- 229910052739 hydrogen Inorganic materials 0.000 claims description 56
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 30
- 229910045601 alloy Inorganic materials 0.000 claims description 22
- 239000000956 alloy Substances 0.000 claims description 22
- 239000012528 membrane Substances 0.000 claims description 21
- 238000000926 separation method Methods 0.000 claims description 16
- 229910052763 palladium Inorganic materials 0.000 claims description 15
- 229910001252 Pd alloy Inorganic materials 0.000 claims description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 239000011733 molybdenum Substances 0.000 claims description 10
- 229910052720 vanadium Inorganic materials 0.000 claims description 10
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 42
- 238000000034 method Methods 0.000 description 17
- 150000002431 hydrogen Chemical class 0.000 description 14
- 229910001182 Mo alloy Inorganic materials 0.000 description 12
- 230000035699 permeability Effects 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000004678 hydrides Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910000946 Y alloy Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- WUJISAYEUPRJOG-UHFFFAOYSA-N molybdenum vanadium Chemical compound [V].[Mo] WUJISAYEUPRJOG-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 1
- UBQALOXXVZQHGR-UHFFFAOYSA-N palladium yttrium Chemical compound [Y].[Pd] UBQALOXXVZQHGR-UHFFFAOYSA-N 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- -1 polymethylsiloxane Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Hydrogen, Water And Hydrids (AREA)
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明は、高純度の水素を分離取得すること
のできる水素分離用合金膜に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to an alloy membrane for hydrogen separation that can separate and obtain high-purity hydrogen.
（従来の技術とその課題）
近年、半導体産業、光フアイバー製造産業など
の発展にともなつて、その製造プロセスにおいて
使用する高純度水素の需要が高まつている。一般
に、水素は天然ガス、ナフサなどの化石燃料を原
料として水蒸気改質法あるいは部分酸化法などに
よつて製造するか、あるいはその他の石油精製プ
ロセス、食塩電解等の副産物として、さらには水
電解によつて製造されてきている。(Prior art and its problems) In recent years, with the development of the semiconductor industry, optical fiber manufacturing industry, etc., the demand for high-purity hydrogen used in the manufacturing process has increased. In general, hydrogen is produced from fossil fuels such as natural gas and naphtha by steam reforming or partial oxidation, or as a byproduct of other petroleum refining processes, salt electrolysis, etc., or by water electrolysis. It has been manufactured ever since.
しかしながら、これらの方法によつて製造した
水素ガス中には、一酸化炭素、二酸化炭素、水蒸
気および炭化水素などの不純物が含有されている
ために、高純度な水素を取得するためにはさらに
水素を分離精製することが必要になつている。 However, since the hydrogen gas produced by these methods contains impurities such as carbon monoxide, carbon dioxide, water vapor, and hydrocarbons, it is necessary to add more hydrogen to obtain high-purity hydrogen. It has become necessary to separate and purify
従来、このような水素の高純度化精製法として
は、エタノールアミン、苛性ソーダなどを用いる
化学吸収法、水、深冷メタノールなどを用いる物
理吸収法、アルミナゲル、モレキユラーシーブ
ス、活性炭などを用いる吸着法、液体窒素、液体
空気などを用いる深冷分離法、ポリメチルシロキ
サン、ポリイミドなどを用いる高分子膜による分
離法、あるいはパラジウム合金膜を用いる拡散性
などが知られている。しかしながら実際には、
99.99999％以上の高純度な水素を取得することの
できる方法としてはパラジウム合金膜を用いる拡
散法しか実用化されていないのが現状である。 Conventionally, such high purity purification methods for hydrogen include chemical absorption methods using ethanolamine, caustic soda, etc., physical absorption methods using water, cryogenic methanol, etc., and alumina gel, molecular sieves, activated carbon, etc. Adsorption methods, cryogenic separation methods using liquid nitrogen, liquid air, etc., separation methods using polymer membranes using polymethylsiloxane, polyimide, etc., and diffusivity methods using palladium alloy membranes are known. However, in reality,
Currently, the only practical method for obtaining hydrogen with a purity of 99.99999% or higher is the diffusion method using a palladium alloy membrane.
このパラジウム合金膜としては、パラジウムに
銀を20〜30％添加した合金膜が代表的なものであ
る。このようにパラジウム合金膜による拡散法
は、高純度水素を取得する方法として現状におい
て唯一の、かつ有用な方法であるが、しかしなが
ら解決すべき課題も残されているのが実状であ
る。すなわち、この合金は低温における水素透過
度が小さいため、水素の分離精製能率を上げるた
めには370℃以上の高温度で使用しなければなら
ないということと、そのうえ極めて高価であると
いう問題がある。 A typical example of this palladium alloy film is an alloy film in which 20 to 30% silver is added to palladium. As described above, the diffusion method using a palladium alloy membrane is currently the only and useful method for obtaining high-purity hydrogen, but the reality is that there are still problems to be solved. That is, this alloy has a low hydrogen permeability at low temperatures, so in order to increase the efficiency of hydrogen separation and purification, it must be used at high temperatures of 370°C or higher, and it is also extremely expensive.
この発明は、従来のパラジウム合金膜からなる
水素分離膜についての問題点を解消し、より低温
域においても高透過度で高純度の水素を分離する
ことができ、しかも安価で耐久性のある水素分離
用合金膜を提供することを目的としている。 This invention solves the problems with conventional hydrogen separation membranes made of palladium alloy membranes, and is capable of separating high-purity hydrogen with high permeability even at lower temperatures, and is an inexpensive and durable hydrogen separation membrane. The purpose is to provide an alloy membrane for separation.
（課題を解決するための手段）
この発明は、前記課題を解決するものとして、
モリブデン10〜50原子％、残部バナジウムからな
る合金膜の表面にパラジウムまたはパラジウム合
金を被覆してなることを特徴とする水素分離用合
金膜を提供する。(Means for Solving the Problems) This invention solves the above problems by:
Provided is an alloy membrane for hydrogen separation, characterized in that the surface of an alloy membrane consisting of 10 to 50 atomic percent molybdenum and the balance vanadium is coated with palladium or a palladium alloy.
モリブデン10〜50原子％、残部バナジウムから
なる合金膜の表面にパラジウム、パラジウム合金
を被覆する手段としては、メツキ法、蒸着法、ス
パツタ法などの適宜なものを採用することができ
る。また、この発明で使用するパラジウム合金と
しては、パラジウム−銀合金（銀20〜30原子％）、
パラジウム−イツトリウム合金（イツトリウム５
〜10原子％）等が挙げられる。 As a means for coating the surface of the alloy film consisting of 10 to 50 atomic percent molybdenum and the balance vanadium with palladium or palladium alloy, an appropriate method such as a plating method, a vapor deposition method, a sputtering method, etc. can be adopted. Further, the palladium alloy used in this invention includes palladium-silver alloy (20 to 30 atomic% silver),
Palladium-yttrium alloy (yttrium 5
~10 atomic%), etc.
もちろん、バナジウム−モリブデンからなる合
金膜、さらにはパラジウムまたはパラジウム合金
被覆膜については、付可避的な不純物元素を排除
するものではない。 Of course, unavoidable impurity elements are not excluded from the alloy film made of vanadium-molybdenum, and further from the palladium or palladium alloy coated film.
合金膜、被覆膜の膜厚についても、操作プロセ
ス、コスト等を考慮して決めることができ、たと
えば、Ｖ−Mo膜を１mm程度とした場合には被覆
層は１〜500nm程度とすることができる。 The thickness of the alloy film and coating film can also be determined by considering the operating process, cost, etc. For example, if the V-Mo film is about 1 mm, the coating layer should be about 1 to 500 nm thick. I can do it.
なお、水素分離用合金膜における水素透過度は
合金中の水素の拡散係数と水素の固溶度の積であ
らわすことができ、バナジウムはパラジウムに比
べて水素の拡散係数、固溶度ともはるかに大き
く、300℃以下におけるバナジウムの水素透過度
はパラジウムのそれに比べて一桁以上も大きい。
しかもその差は低温ほど大きい。しかしながら、
バナジウムは低い水素圧で多量の水素を吸収し、
また200℃以下では水素化物を形成し水素脆性を
起し易い。更に酸化し易く、その表面に水素透過
の障害となる安定な酸化膜を形成するので、その
ままでは水素分離膜として使用できない。 The hydrogen permeability in an alloy membrane for hydrogen separation can be expressed as the product of the diffusion coefficient of hydrogen in the alloy and the solid solubility of hydrogen, and vanadium has a much higher diffusion coefficient and solid solubility of hydrogen than palladium. The hydrogen permeability of vanadium at temperatures below 300°C is more than an order of magnitude higher than that of palladium.
Moreover, the difference is larger at lower temperatures. however,
Vanadium absorbs a large amount of hydrogen at low hydrogen pressure,
Furthermore, at temperatures below 200°C, hydrides are formed and hydrogen embrittlement is likely to occur. Furthermore, it is easily oxidized and forms a stable oxide film on its surface that impedes hydrogen permeation, so it cannot be used as it is as a hydrogen separation membrane.
そこでこの発明は、バナジウムにモリブデンを
10〜50原子％の範囲で添加して合金膜とすると、
バナジウムの水素透過度を大きく減ずることな
く、水素脆性が改善され、水素分離用合金膜とし
て使用でき、さらには、この合金膜の表面にパラ
ジウムあるいはパラジウム合金を被覆すると、耐
酸化性となると共に、200℃以上で使用するとバ
ナジウムおよびモリブデンがパラジウム皮膜に拡
散し、これにより硬化し水素脆性を起し難しくな
るとの知見に基づいて完成されている。 Therefore, this invention added molybdenum to vanadium.
When added in the range of 10 to 50 atomic% to form an alloy film,
The hydrogen embrittlement of vanadium is improved without greatly reducing its hydrogen permeability, and it can be used as an alloy membrane for hydrogen separation.Furthermore, when the surface of this alloy membrane is coated with palladium or a palladium alloy, it becomes oxidation resistant and This work was completed based on the knowledge that vanadium and molybdenum diffuse into the palladium film when used at temperatures above 200°C, which causes it to harden and cause hydrogen embrittlement, making it difficult to use.
以上のことから明らかなように、この発明にお
けるパラジウム合金のモリブデン量が10原子％未
満では水素脆性を改善できず、またモリブデン量
が50原子％を超えると合金中の水素の固溶度が小
さくなり、水素透過度が小さくなる。しかも高融
点の成分であるモリブデン量が多くなるため溶製
が困難となる。このようなことから、この発明に
おいては、モリブデンの量を10〜50原子％の範囲
とする。 As is clear from the above, hydrogen embrittlement cannot be improved if the amount of molybdenum in the palladium alloy in this invention is less than 10 atomic percent, and if the amount of molybdenum exceeds 50 atomic percent, the solid solubility of hydrogen in the alloy becomes small. Therefore, the hydrogen permeability becomes smaller. Moreover, the amount of molybdenum, which is a component with a high melting point, increases, making melting difficult. For this reason, in the present invention, the amount of molybdenum is set in the range of 10 to 50 atomic %.
次にこの発明の実施例を示す。 Next, examples of this invention will be shown.
（実施例 １〜３）
アルゴン中のアーク溶融法によりＶ−10原子％
Mo合金（実施例１）、Ｖ−20原子％Mo合金（実
施例２）およびＶ−30原子％Mo合金（実施例
３）を溶製し、熱間圧延により、厚さ約１mmの膜
とした。これらの膜の表面に電解メツキ法により
厚さ10nmのパラジウム被覆を行つた。(Examples 1 to 3) V-10 atomic% by arc melting method in argon
Mo alloy (Example 1), V-20 atomic% Mo alloy (Example 2) and V-30 atomic% Mo alloy (Example 3) were melted and hot rolled to form a film with a thickness of about 1 mm. did. The surfaces of these films were coated with palladium to a thickness of 10 nm by electrolytic plating.
この各々についての水素透過度の温度依存性を
示したものが第１図である。図中の曲線１はＶ−
10原子％Mo合金（実施例１）、曲線２はＶ−20
原子％Mo合金（実施例２）を、曲線３はＶ−30
原子％Mo合金（実施例３）を示している。な
お、曲線４は比較のためのパラジウムのみからな
る膜の場合を示したものである。この結果が示す
ように、実施例１〜３の水素分離用合金膜の水素
透過度（曲線１〜３）は、パラジウム膜のみの場
合（曲線４）よりも大きいことが分る。 FIG. 1 shows the temperature dependence of hydrogen permeability for each of these. Curve 1 in the figure is V-
10 atomic% Mo alloy (Example 1), curve 2 is V-20
atomic% Mo alloy (Example 2), curve 3 is V-30
Atomic % Mo alloy (Example 3) is shown. Note that curve 4 shows the case of a film made only of palladium for comparison. As shown in the results, the hydrogen permeability of the hydrogen separation alloy membranes of Examples 1 to 3 (curves 1 to 3) is higher than that of the palladium membrane alone (curve 4).
また、Ｖ−20原子％Mo合金（実施例２）につ
いて300℃以上で、１気圧の水素圧下で水素透過
試験を行つたが、亀裂は発生しなかつた。 Further, a hydrogen permeation test was conducted on the V-20 atomic % Mo alloy (Example 2) at a temperature of 300° C. or higher and under a hydrogen pressure of 1 atmosphere, but no cracks were observed.
（実施例 ４〜５）
アルゴン中のアーク溶解法によりＶ−10原子％
Mo合金（実施例４）およびＶ−20原子％Mo合
金（実施例５）を溶製し、その水素圧力−組成等
温曲線を測定した。その結果を示したものが第２
図である。図中の４ａ，４ｂ曲線は、各々、300
℃におけるＶ−10原子％Mo合金（実施例４）の
吸収曲線と放出曲線を示し、また、曲線５ａ，５
ｂは、Ｖ−20原子％Mo合金（実施例５）の吸収
曲線と放出曲線を示している。いずれの水素圧力
−組成等温曲線においても一定の水素圧で急激に
水素濃度が増大する、いわゆるプラトーが認めら
れないことから、試験温度−圧力範囲において水
素化物が形成されないことがわかる。すなわち、
この合金は水素脆性を起しにくいことがわかる。
また、両合金とも水素吸収・放出曲線において大
きな違いが認められない。ヒステリシスが小さい
ことから、水素吸収、放出過程において塑性変形
が殆んど起らず、水素透過を繰返しても性能が劣
化しないことを示している。(Examples 4-5) V-10 atomic% by arc melting method in argon
A Mo alloy (Example 4) and a V-20 atomic % Mo alloy (Example 5) were melted and their hydrogen pressure-composition isotherm curves were measured. The second one shows the results.
It is a diagram. Curves 4a and 4b in the figure are each 300
The absorption and emission curves of the V-10 atomic% Mo alloy (Example 4) at °C are shown, and curves 5a and 5
b shows the absorption and emission curves of the V-20 atomic % Mo alloy (Example 5). Since no so-called plateau, in which the hydrogen concentration rapidly increases at a constant hydrogen pressure, is observed in any of the hydrogen pressure-composition isothermal curves, it can be seen that hydrides are not formed in the test temperature-pressure range. That is,
It can be seen that this alloy is less susceptible to hydrogen embrittlement.
Furthermore, no major difference was observed in the hydrogen absorption/release curves for both alloys. The small hysteresis indicates that almost no plastic deformation occurs during the hydrogen absorption and release process, and the performance does not deteriorate even after repeated hydrogen permeation.
（発明の効果）
以上詳しく説明したように、この発明の合金膜
は、水素透過度がパラジウムのみからなる膜より
もはるかに大きいため、水素分離を高効率で行う
ことができ、200℃のような低温においても大き
な水素透過度を示すことから、水素分離を省エネ
ルギーで行うことを可能とする。また、水素化物
を形成しないので水素脆性が起らず、水素の吸
収・放出過程において塑性変形が起らないので耐
久性に優れている。(Effects of the Invention) As explained in detail above, the alloy membrane of the present invention has a much higher hydrogen permeability than a membrane made only of palladium, and therefore can perform hydrogen separation with high efficiency, such as at 200°C. It exhibits high hydrogen permeability even at low temperatures, making it possible to perform hydrogen separation with energy savings. Furthermore, since no hydride is formed, hydrogen embrittlement does not occur, and plastic deformation does not occur during the hydrogen absorption/release process, resulting in excellent durability.
さらに、合金皮膜表面にパラジウムまたはパラ
ジウム合金膜が被覆されているので炭素、オイル
ミストなどの付着による水素分離性能の劣化は、
200〜300℃で空気を導入するベーキング処理によ
り簡単に回復することができるため高能率操業が
可能である。 Furthermore, since the surface of the alloy film is coated with palladium or palladium alloy film, deterioration of hydrogen separation performance due to adhesion of carbon, oil mist, etc.
High-efficiency operation is possible because it can be easily recovered by baking treatment that introduces air at 200 to 300°C.
さらに、バナジウムはパラジウムの約1/10、モ
リブデンは約1/300の価格であるので、既存のパ
ラジウム合金膜に比較してはるかに安価でもあ
る。 Furthermore, since vanadium is about 1/10th the price of palladium and molybdenum is about 1/300th the price, it is also much cheaper than existing palladium alloy membranes.
第１図は、この発明の実施例と比較例との水素
透過度と温度の関係を示した相関図である。第２
図は、この発明のＶ−Mo合金の300℃における
水素圧力と組成等温線を示した相関図である。
FIG. 1 is a correlation diagram showing the relationship between hydrogen permeability and temperature in an example of the present invention and a comparative example. Second
The figure is a correlation diagram showing the hydrogen pressure and composition isotherm at 300° C. of the V-Mo alloy of the present invention.
Claims (1)
らなる合金膜表面に、パラジウムまたはパラジウ
ム合金を被覆してなることを特徴とする水素分離
用合金膜。1. An alloy membrane for hydrogen separation, characterized in that the surface of an alloy membrane consisting of 10 to 50 atomic percent molybdenum and the balance vanadium is coated with palladium or a palladium alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8469389A JPH02265631A (en) | 1989-04-05 | 1989-04-05 | Alloy film for separation of hydrogen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8469389A JPH02265631A (en) | 1989-04-05 | 1989-04-05 | Alloy film for separation of hydrogen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02265631A JPH02265631A (en) | 1990-10-30 |
| JPH0579367B2 true JPH0579367B2 (en) | 1993-11-02 |
Family
ID=13837747
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8469389A Granted JPH02265631A (en) | 1989-04-05 | 1989-04-05 | Alloy film for separation of hydrogen |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02265631A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2106838A1 (en) | 2008-03-24 | 2009-10-07 | The Japan Steel Works, Ltd. | Hydrogen permeable module and usage thereof |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5776353A (en) * | 1996-02-16 | 1998-07-07 | Advanced Minerals Corporation | Advanced composite filtration media |
| JP2003305346A (en) * | 2002-04-11 | 2003-10-28 | Toyo Kohan Co Ltd | Separation film laminate and production method for component using the same |
| KR20090110897A (en) | 2007-02-19 | 2009-10-23 | 미츠비시 가스 가가쿠 가부시키가이샤 | Hydrogen Purification Method, Hydrogen Separator and Hydrogen Purifier |
| JP5594017B2 (en) * | 2010-09-24 | 2014-09-24 | 東京瓦斯株式会社 | Hydrogen separation method and apparatus |
| WO2012039283A1 (en) * | 2010-09-24 | 2012-03-29 | 東京瓦斯株式会社 | Hydrogen-separating membrane |
| JP5745662B2 (en) * | 2014-03-10 | 2015-07-08 | 東京瓦斯株式会社 | Two-stage hydrogen separation reformer |
-
1989
- 1989-04-05 JP JP8469389A patent/JPH02265631A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2106838A1 (en) | 2008-03-24 | 2009-10-07 | The Japan Steel Works, Ltd. | Hydrogen permeable module and usage thereof |
| US8075670B2 (en) | 2008-03-24 | 2011-12-13 | The Japan Steel Works, Ltd. | Hydrogen permeable module and usage thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02265631A (en) | 1990-10-30 |
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