JPH1199323A - High performance hydrogen separation membrane - Google Patents
High performance hydrogen separation membraneInfo
- Publication number
- JPH1199323A JPH1199323A JP26349497A JP26349497A JPH1199323A JP H1199323 A JPH1199323 A JP H1199323A JP 26349497 A JP26349497 A JP 26349497A JP 26349497 A JP26349497 A JP 26349497A JP H1199323 A JPH1199323 A JP H1199323A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- separation membrane
- alloy
- hydrogen separation
- high performance
- 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.)
- Granted
Links
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- Separation Using Semi-Permeable Membranes (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、優れた水素透過性
能及び高温強度を有する水素分離膜に関する。The present invention relates to a hydrogen separation membrane having excellent hydrogen permeation performance and high-temperature strength.
【０００２】[0002]
【従来の技術】水素を含む混合ガスから水素を選択的に
透過するＰｄ合金水素分離膜は高純度水素の製造装置へ
の適用が考えられている。現在、水素分離膜は、純Ｐｄ
やＰｄ−２４ａｔ％Ａｇ合金からなる膜が使用されてい
る。純Ｐｄ膜は水素化物を生成して脆化を起こし、ま
た、水素分離膜の使用温度である５５０℃程度の高温に
おける強度が十分でないという問題点があった。2. Description of the Related Art A Pd alloy hydrogen separation membrane which selectively permeates hydrogen from a mixed gas containing hydrogen is considered to be applied to an apparatus for producing high-purity hydrogen. At present, hydrogen separation membrane is pure Pd
And a film made of a Pd-24 at% Ag alloy. The pure Pd film has a problem that hydrides are generated to cause embrittlement, and that the strength at a high temperature of about 550 ° C., which is the operating temperature of the hydrogen separation membrane, is not sufficient.
【０００３】[0003]
【発明が解決しようとする課題】そこで、本発明では、
上記の問題点を解消し、高い水素透過性能及び高温強度
を備えた水素分離膜を提供しようとするものである。Therefore, in the present invention,
An object of the present invention is to solve the above problems and provide a hydrogen separation membrane having high hydrogen permeation performance and high-temperature strength.
【０００４】[0004]
【問題点を解決するための手段】本発明は、Ｐｄ又はＰ
ｄ−Ａｇ合金を主成分とする高性能水素分離膜におい
て、Ｙ、Ｇｄ及びＬｕの群から選択される１種以上の希
土類元素を３ａｔ％以上含有し、該希土類元素の含有量
をｙａｔ％、Ａｇの含有量をｘａｔ％とするときに、３
６≧３ｙ＋ｘ≧２４ の領域の合金で高性能水素分離膜
を構成することにより、上記の課題の解決に成功した。SUMMARY OF THE INVENTION The present invention relates to Pd or Pd.
The high performance hydrogen separation membrane containing a d-Ag alloy as a main component contains at least 3 at% of one or more rare earth elements selected from the group consisting of Y, Gd and Lu, and the content of the rare earth elements is atat%, When the content of Ag is xat%, 3
The above problem was successfully solved by forming a high-performance hydrogen separation membrane with an alloy in the range of 6 ≧ 3y + x ≧ 24.
【０００５】[0005]
【発明の実施の形態】本発明は、Ｐｄ又はＰｄ−Ａｇ合
金を主成分とする水素分離膜であって、Ｙ、Ｇｄ及びＬ
ｕの群から選択される１種以上の希土類元素を３ａｔ％
以上添加して優れた水素透過性能及び高温強度の確保に
成功したものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a hydrogen separation membrane containing Pd or a Pd-Ag alloy as a main component, wherein Y, Gd and L
3 at% of at least one rare earth element selected from the group of u
With the above addition, excellent hydrogen permeation performance and high-temperature strength were successfully ensured.
【０００６】詳しくは、上記希土類元素の含有量をｙａ
ｔ％、Ａｇの含有量をｘａｔ％とするときに、水素分離
膜の合金組成のうち、Ａｇと希土類元素の含有量が、３
ｙ＋ｘ≧２４の関係を満たすことにより、室温以上の温
度領域において水素化物（β相）の生成による水素脆化
を防止し、３ｙ＋ｘ≦３６の関係を満たすことにより、
上記合金中にＰｄ3 （Ｙ，Ｇｄ，Ｌｕ）等の金属間化合
物が第２相として析出するのを抑制して２相分離の発生
を防止し、水素透過性能の低下をなくしたものである。Specifically, the content of the rare earth element is set to ya
When the content of Ag and the rare earth element in the alloy composition of the hydrogen separation membrane are 3% and the content of Ag is xat%,
By satisfying the relationship of y + x ≧ 24, hydrogen embrittlement due to the formation of hydride (β phase) is prevented in a temperature range of room temperature or higher, and by satisfying the relationship of 3y + x ≦ 36,
This is to prevent the intermetallic compound such as Pd 3 (Y, Gd, Lu) from being precipitated as a second phase in the above alloy, to prevent the occurrence of two-phase separation, and to prevent a decrease in hydrogen permeation performance. .
【０００７】図１は、本発明の水素分離膜に用いる合金
の組成範囲を示したグラフである。図中、３ｙ＋ｘ＞３
６の範囲は２相分離域を示し、３ｙ＋ｘ＜２４の範囲は
水素化物（β相）の生成域を示す。したがって、本発明
の合金組成は、図中に斜線部分として表記した範囲であ
る。FIG. 1 is a graph showing the composition range of the alloy used for the hydrogen separation membrane of the present invention. In the figure, 3y + x> 3
The range of 6 indicates a two-phase separation zone, and the range of 3y + x <24 indicates a hydride (β phase) generation zone. Therefore, the alloy composition of the present invention is in the range indicated by the hatched portion in the figure.
【０００８】[0008]
【実施例】以下、本発明の水素分離膜を作製し、膜性能
及び希土類元素の添加効果を調べた。供試材は、Ｐｄ及
びＰｄ−Ａｇに対するＹ、Ｇｄ、Ｌｕの配合量を表１に
示すように変化させ、Ａｒガス雰囲気中でアークで溶解
した。その後、４段式小型ロール圧延機で膜厚０．１〜
０．２ｍｍの金属膜を作製した。得られた金属膜は、
水素透過性能評価、耐水素脆化性評価、及び高温強
度特性評価を行った。結果は表１に示した。EXAMPLES Hereinafter, a hydrogen separation membrane of the present invention was manufactured, and the membrane performance and the effect of adding a rare earth element were examined. The test materials were melted by arc in an Ar gas atmosphere while changing the amounts of Y, Gd and Lu with respect to Pd and Pd-Ag as shown in Table 1. After that, the film thickness is 0.1 ~
A 0.2 mm metal film was produced. The obtained metal film is
Hydrogen permeation performance evaluation, hydrogen embrittlement resistance evaluation, and high temperature strength characteristic evaluation were performed. The results are shown in Table 1.
【０００９】水素透過性能評価 水素透過試験は、金属膜を試験用セルにセットし、温度
７７３Ｋで試験用セルの片側に１００％の水素ガスを流
し、反対側に透過した水素のガス流量を測定した。水素
透過性能は、次式で示す水素透過係数Ｋ値の比較で評価
した。 Ｖ＝Ｋ（Ｐ1 1/2 −Ｐ2 1/2 ）×（１／ｔ） 式中、Ｖ：水素透過速度〔ｍ3 ／ｍ2 ・ｓ〕 Ｋ：水素透過係数〔ｍ3 ・ｍ／ｍ2 ・ｓ・Ｐａ1/2 〕 Ｐ1 ：１次側（入口側）水素分圧〔Ｐａ〕 Ｐ2 ：２次側（出口側）水素分圧〔Ｐａ〕 ｔ：膜厚〔ｍ〕Evaluation of hydrogen permeation performance In the hydrogen permeation test, a metal film was set in a test cell, 100% hydrogen gas was flowed to one side of the test cell at a temperature of 773K, and the flow rate of hydrogen permeated to the other side was measured. did. The hydrogen permeation performance was evaluated by comparing a hydrogen permeation coefficient K value represented by the following equation. V = K (P 1 1/2 −P 2 1/2 ) × (1 / t) where V: hydrogen permeability [m 3 / m 2 · s] K: hydrogen permeability [m 3 · m / m 2 · s · Pa 1/2 ] P 1 : Partial pressure of hydrogen on the primary side (inlet side) [Pa] P 2 : Partial pressure of hydrogen on the secondary side (outlet side) [Pa] t: Film thickness [m]
【００１０】耐水素脆化性評価 耐水素脆化性評価は、金属膜の合金に水素を固溶させた
状態でＸ線回折分析を行って調べた。各金属膜を水素圧
０．１ＭＰａ、２９３Ｋの下で水素をチャージして最も
水素化物を生成しやすい状態であるＨ（水素原子）／Ｍ
（金属原子）（モル比）＝０．２／０．３にしてＸ線回
折分析を行った。Evaluation of hydrogen embrittlement resistance The hydrogen embrittlement resistance was evaluated by performing X-ray diffraction analysis in a state where hydrogen was dissolved in the metal film alloy. Each metal film is charged with hydrogen under a hydrogen pressure of 0.1 MPa and 293 K, and is in a state in which hydride is most easily generated by hydrogen (H) / M.
X-ray diffraction analysis was performed with (metal atom) (molar ratio) = 0.2 / 0.3.
【００１１】高温強度特性評価 高温強度特性評価は、７７３Ｋにおける高温引張試験に
よって評価した。引張試験は、精密万能試験機を用いて
大気中で行った。取得データは、引張強さ（σB ）、
０．２％耐力（σ0.2 ）、及び破断伸び（δ）である。Evaluation of High Temperature Strength Properties High temperature strength properties were evaluated by a high temperature tensile test at 773K. The tensile test was performed in the air using a precision universal testing machine. The acquired data are tensile strength (σ B ),
0.2% proof stress (σ 0.2 ) and elongation at break (δ).
【００１２】比較のために、表１に記載の従来合金及び
比較合金を作製し、上記実施例の合金と同様に評価し、
その結果も表１に示した。Ｐｄ及びＰｄ−２４ａｔ％Ａ
ｇ合金（Ｎｏ．７及びＮｏ．６）を基準にして他の合金
をみると、３ａｔ％以上のＹ、Ｇｄ、Ｌｕを添加したＮ
ｏ．１〜５の合金（本発明の実施例）では、水素透過性
能が高く、特に、８ａｔ％Ｇｄ添加合金（Ｎｏ．２）は
Ｐｄ−２４ａｔ％Ａｇ合金（Ｎｏ．６）の２倍以上の水
素透過性能を示した。For comparison, conventional alloys and comparative alloys shown in Table 1 were prepared and evaluated in the same manner as the alloys of the above examples.
The results are also shown in Table 1. Pd and Pd-24at% A
Looking at other alloys based on the g alloy (No. 7 and No. 6), N containing 3 at% or more of Y, Gd, and Lu was added.
o. The alloys Nos. 1 to 5 (Examples of the present invention) have high hydrogen permeation performance, and in particular, the 8 at% Gd-added alloy (No. 2) is twice or more hydrogen than the Pd-24 at% Ag alloy (No. 6). The transmission performance was shown.
【００１３】また、高温強度についても、Ｙ、Ｇｄを添
加することにより、Ｐｄ−２４ａｔ％Ａｇ合金（Ｎｏ．
６）に比べて、３ａｔ％添加したＮｏ．４及びＮｏ．５
の合金で２倍、８ａｔ％添加したＮｏ．１及びＮｏ．２
の合金で３倍以上の高温強度が得られた。[0013] With respect to the high temperature strength, the addition of Y and Gd also makes it possible to obtain a Pd-24 at% Ag alloy (No.
No. 6 in which 3 at% was added compared to No. 6). 4 and No. 4. 5
No. 2 which is twice as much as the alloy of No. 8 at. 1 and No. 1 2
3 times or more high-temperature strength was obtained with the alloy No.
【００１４】なお、Ａｇを含有しない比較材のＮｏ．８
合金は、Ｙの添加量が６ａｔ％と少ないため、本発明の
３ｙ＋ｘ≧２４の範囲から外れ、水素化物生成による水
素脆化が発生した。また、Ｎｏ．９及びＮｏ．１０の合
金は、Ｙの添加量が多いため、本発明の３６≧３ｙ＋ｘ
の範囲から外れ、Ｐｄ3 Ｙ金属間化合物からなる第２相
が析出して２相分離状態を起こして、水素透過性能が低
下した。The comparative material containing no Ag was no. 8
Since the addition amount of Y was as small as 6 at%, the alloy was out of the range of 3y + x ≧ 24 of the present invention, and hydrogen embrittlement due to hydride generation occurred. In addition, No. 9 and No. 9 Alloy No. 10 contains a large amount of Y, so that 36 ≧ 3y + x
Out of the range, the second phase composed of the Pd 3 Y intermetallic compound was precipitated to cause a two-phase separation state, and the hydrogen permeation performance was reduced.
【００１５】[0015]
【表１】 [Table 1]
【００１６】[0016]
【発明の効果】本発明は、上記の構成を採用することに
より、優れた水素透過性能と高温強度を備えた水素分離
膜の提供を可能にし、高純度水素製造装置を初めとする
用途の拡大を可能にするものである。According to the present invention, by employing the above-described structure, it is possible to provide a hydrogen separation membrane having excellent hydrogen permeation performance and high-temperature strength, and to expand applications of the apparatus including a high-purity hydrogen production apparatus. Is what makes it possible.
【図１】本発明の水素分離膜に用いる合金の組成範囲を
示したグラフである。FIG. 1 is a graph showing a composition range of an alloy used for a hydrogen separation membrane of the present invention.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小林 一登 広島県広島市西区観音新町四丁目６番22号 三菱重工業株式会社広島研究所内 ──────────────────────────────────────────────────の Continuing from the front page (72) Inventor Kazuto Kobayashi Hiroshima Pref. Hiroshima Pref.
Claims (1)
高性能水素分離膜において、Ｙ、Ｇｄ及びＬｕの群から
選択される１種以上の希土類元素を３ａｔ％以上含有
し、該希土類元素の含有量をｙａｔ％、Ａｇの含有量を
ｘａｔ％とするときに、３６≧３ｙ＋ｘ≧２４ の領域
の合金からなることを特徴とする高性能水素分離膜。1. A high-performance hydrogen separation membrane containing Pd or a Pd—Ag alloy as a main component, wherein at least 3 at% or more of one or more rare earth elements selected from the group consisting of Y, Gd, and Lu are contained. A high performance hydrogen separation membrane comprising an alloy in the range of 36 ≧ 3y + x ≧ 24, where y is the content of yat% and x is the content of Ag.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26349497A JP3377731B2 (en) | 1997-09-29 | 1997-09-29 | High performance hydrogen separation membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26349497A JP3377731B2 (en) | 1997-09-29 | 1997-09-29 | High performance hydrogen separation membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1199323A true JPH1199323A (en) | 1999-04-13 |
| JP3377731B2 JP3377731B2 (en) | 2003-02-17 |
Family
ID=17390309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26349497A Expired - Lifetime JP3377731B2 (en) | 1997-09-29 | 1997-09-29 | High performance hydrogen separation membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3377731B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6759430B2 (en) * | 1998-01-22 | 2004-07-06 | Oxon Medica Inc. | Piperidine and pyrrolidine derivatives comprising a nitric oxide donor for treating stress |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2156883B1 (en) | 2007-06-11 | 2016-03-30 | NGK Insulators, Ltd. | Method for producing hydrogen separation membrane and selectively permeable membrane reactor |
-
1997
- 1997-09-29 JP JP26349497A patent/JP3377731B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6759430B2 (en) * | 1998-01-22 | 2004-07-06 | Oxon Medica Inc. | Piperidine and pyrrolidine derivatives comprising a nitric oxide donor for treating stress |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3377731B2 (en) | 2003-02-17 |
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