JP2011202258A - Hydrogen permeable alloy and hydrogen permeation membrane utilizing the same - Google Patents
Hydrogen permeable alloy and hydrogen permeation membrane utilizing the same Download PDFInfo
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Abstract
Description
本発明は、水素透過性合金及びこれを利用した水素透過膜に関し、より詳細には水素透過性Ｃｕ−Ｐｄ合金及びこれを利用した水素透過膜に関する。 The present invention relates to a hydrogen permeable alloy and a hydrogen permeable membrane using the same, and more particularly to a hydrogen permeable Cu-Pd alloy and a hydrogen permeable membrane using the same.
水素の用途は広く、例えば石油精製分野では脱硫剤として、化学工業分野ではアンモニアやメタノールをはじめとする各種化学品の原料として、半導体分野では還元雰囲気ガスとして、燃料電池分野では燃料として利用されている。 Hydrogen is widely used, for example, as a desulfurization agent in the petroleum refining field, as a raw material for various chemicals including ammonia and methanol in the chemical industry field, as a reducing atmosphere gas in the semiconductor field, and as a fuel in the fuel cell field. Yes.
水素の製造技術としては、炭化水素や石炭から水素を製造する水蒸気改質法が知られており、例えば金属触媒下、７００〜８００℃の高温で水蒸気をメタンと反応させ、一酸化炭素と水素を得るという方法である。一酸化炭素は更にシフト反応により、二酸化炭素に変換される。水素及び副生成物を含む混合ガスから水素を分離・精製する方法としては水素透過膜を利用する方法が知られている。水素透過膜は水素のみを選択的に透過する特性を有しており、水素透過膜の一方の面（一次側）に対して混合ガスで加圧すると、水素だけが水素透過膜中に溶け込んで拡散し、反対側の面（二次側）に到達することができる。このようにして混合ガスから水素を分離することにより、水素を高純度に精製できる。 As a hydrogen production technique, a steam reforming method for producing hydrogen from hydrocarbons or coal is known. For example, steam is reacted with methane at a high temperature of 700 to 800 ° C. under a metal catalyst to produce carbon monoxide and hydrogen. It is a method of getting. Carbon monoxide is further converted to carbon dioxide by a shift reaction. As a method for separating and purifying hydrogen from a mixed gas containing hydrogen and by-products, a method using a hydrogen permeable membrane is known. The hydrogen permeable membrane has a characteristic of selectively permeating only hydrogen. When one side (primary side) of the hydrogen permeable membrane is pressurized with a mixed gas, only hydrogen is dissolved into the hydrogen permeable membrane. It can diffuse and reach the opposite surface (secondary side). By separating hydrogen from the mixed gas in this way, hydrogen can be purified with high purity.
最近では、水素透過膜と改質器を組み合わせることで、水素の生成反応と水素の分離・精製を同時に行うメンブレンリフォーマー技術の開発が進んでいる。これは、シフト反応器や一酸化炭素の選択除去を必要としないことから新たな水素製造方法として期待されている技術であり、改質触媒を利用して５５０〜６５０℃程度の従来に比べて低温でしかも高い改質効率で改質反応を進行させることができるという利点がある。 Recently, development of membrane reformer technology that simultaneously performs hydrogen generation reaction and hydrogen separation and purification by combining a hydrogen permeable membrane and a reformer has been progressing. This is a technology that is expected as a new hydrogen production method because it does not require a shift reactor or selective removal of carbon monoxide. Compared to the conventional technology of about 550 to 650 ° C. using a reforming catalyst. There is an advantage that the reforming reaction can proceed at a low temperature and with high reforming efficiency.
パラジウムは水素の選択透過性を有していることから、水素透過膜の材料としてパラジウムを主体とする合金が使用されており、その中でもＰｄ−Ｃｕ合金というのが知られている。特表２００２−５３９９１８号公報（特許文献１）では６０重量％のパラジウムと４０重量％の銅の合金を水素透過膜として使用したことが記載されている。特開２００１−２６２２５２号公報（特許文献２）では、Ｐｄを主成分としてＣｕを０〜２０ａｔ％添加することで水素脆化を抑制することが記載されている。特開２００４−１７４３７３号公報（特許文献３）ではＣｕはＰｄを合金化して強度を向上させ、水素脆化を抑制する効果があり、水素ガスが４００℃以上になりうる水素ガス精製・分離装置に適用するには、高温強度を維持できるようにＰｄを主成分としてＣｕを１〜４０ａｔ％含んだ合金組成とすることが好ましいとされている。 Since palladium has hydrogen permselectivity, an alloy mainly composed of palladium is used as a material for the hydrogen permeable membrane, and among these, a Pd—Cu alloy is known. JP-T-2002-539918 (Patent Document 1) describes that an alloy of 60% by weight of palladium and 40% by weight of copper was used as a hydrogen permeable membrane. Japanese Patent Application Laid-Open No. 2001-262252 (Patent Document 2) describes that hydrogen embrittlement is suppressed by adding 0 to 20 at% of Cu containing Pd as a main component. In Japanese Patent Application Laid-Open No. 2004-174373 (Patent Document 3), Cu has an effect of alloying Pd to improve strength and suppress hydrogen embrittlement, and a hydrogen gas purification / separation apparatus in which hydrogen gas can be 400 ° C. or higher. For example, it is preferable to use an alloy composition containing Pd as a main component and Cu in an amount of 1 to 40 at% so that high temperature strength can be maintained.
上記先行技術文献に記載されているように、Ｐｄ−Ｃｕ合金は水素透過膜用の材料として有望であるが、Ｐｄ−Ｃｕ合金は高温下における水素透過性が極端に低下するという問題がある。すなわち、Ｐｄ−Ｃｕ合金は５００℃程度までは水素透過性に大きな変化は見られないが、６００℃近くまで加熱すると一桁近くも水素透過係数が減少する。 As described in the above-mentioned prior art documents, Pd—Cu alloys are promising as materials for hydrogen permeable membranes, but Pd—Cu alloys have a problem that hydrogen permeability at high temperatures is extremely lowered. That is, the Pd—Cu alloy shows no significant change in hydrogen permeability up to about 500 ° C., but when heated to near 600 ° C., the hydrogen permeability coefficient decreases by almost an order of magnitude.
上述したように、水素製造のための改質反応は高温で行う必要があることから、高温下における水素透過率は特に優れていることが望ましい。特に６００℃付近というのはメンブレンリフォーマー技術の実用化を進める上でも重要であることから、この温度付近における水素透過率を高める必要性が存在する。 As described above, since the reforming reaction for producing hydrogen needs to be performed at a high temperature, it is desirable that the hydrogen permeability at a high temperature is particularly excellent. In particular, the vicinity of 600 ° C. is important in promoting the practical application of membrane reformer technology, and therefore there is a need to increase the hydrogen permeability in the vicinity of this temperature.
そこで、本発明は高温下での水素透過率に優れたＣｕ−Ｐｄ合金を提供することを課題の一つとする。また、本発明はそのようなＣｕ−Ｐｄ合金を材料とした水素透過膜を提供することを別の課題の一つとする。また、本発明はそのような水素透過膜を利用した水素含有ガスからの水素分離方法を提供することを更に別の課題の一つとする。 Thus, an object of the present invention is to provide a Cu—Pd alloy having excellent hydrogen permeability at high temperatures. Another object of the present invention is to provide a hydrogen permeable membrane made of such a Cu—Pd alloy. Another object of the present invention is to provide a method for separating hydrogen from a hydrogen-containing gas using such a hydrogen permeable membrane.
本発明者は上記課題を解決すべく鋭意研究を重ねたところ、所定の組成をもつＣｕ−Ｐｄ合金に対してアルミニウムを所定量含有させることで、高温特性が有意に改善することを見出した。 The present inventor has conducted extensive research to solve the above problems, and has found that high temperature characteristics are significantly improved by adding a predetermined amount of aluminum to a Cu—Pd alloy having a predetermined composition.
上記知見を基礎として完成した本発明は一側面において、Ｃｕ、Ｐｄ及びＡｌで構成される水素透過性銅合金であり、Ｃｕ、Ｐｄ及びＡｌの原子濃度（ａｔ％）をそれぞれ［Ｃｕ］、［Ｐｄ］及び［Ａｌ］とすると、［Ｐｄ］／（［Ｃｕ］＋［Ｐｄ］）＝４１〜５０％、［Ａｌ］／（［Ｃｕ］＋［Ｐｄ］）＝０．０５〜４．０％であって、式：［Ａｌ］／（［Ｃｕ］＋［Ｐｄ］）≦（２／９）×［Ｐｄ］／（［Ｃｕ］＋［Ｐｄ］）−（０．６４／９）
の関係を満たす水素透過性銅合金である。
The present invention completed on the basis of the above knowledge is, in one aspect, a hydrogen permeable copper alloy composed of Cu, Pd, and Al, and the atomic concentrations (at%) of Cu, Pd, and Al are set to [Cu], [ When Pd] and [Al], [Pd] / ([Cu] + [Pd]) = 41-50%, [Al] / ([Cu] + [Pd]) = 0.05-4.0% And the formula: [Al] / ([Cu] + [Pd]) ≦ (2/9) × [Pd] / ([Cu] + [Pd]) − (0.64 / 9)
It is a hydrogen-permeable copper alloy that satisfies the relationship
本発明に係る水素透過性銅合金は一実施形態において、［Ｐｄ］／（［Ｃｕ］＋［Ｐｄ］）＝４４〜４７％、［Ａｌ］／（［Ｃｕ］＋［Ｐｄ］）＝０．４〜１．５％である。 In one embodiment, the hydrogen permeable copper alloy according to the present invention has [Pd] / ([Cu] + [Pd]) = 44 to 47%, [Al] / ([Cu] + [Pd]) = 0. 4 to 1.5%.
本発明は別の一側面において、本発明に係る銅合金でできた水素透過膜である。 In another aspect, the present invention is a hydrogen permeable membrane made of the copper alloy according to the present invention.
本発明に係る水素透過膜は一実施形態において、厚みが１〜２００μｍである。 In one embodiment, the hydrogen permeable membrane according to the present invention has a thickness of 1 to 200 μm.
本発明は別の一側面において、水素含有ガスが本発明に係る水素透過膜を通過する工程を含む水素含有ガスからの水素分離方法である。 In another aspect, the present invention is a method for separating hydrogen from a hydrogen-containing gas, including a step of allowing the hydrogen-containing gas to pass through the hydrogen-permeable membrane according to the present invention.
本発明に係る水素分離方法は一実施形態において、水素含有ガスが本発明に係る水素透過膜を５５０〜６５０℃の温度で通過する工程を含む。 In one embodiment, the hydrogen separation method according to the present invention includes a step in which a hydrogen-containing gas passes through the hydrogen permeable membrane according to the present invention at a temperature of 550 to 650 ° C.
本発明によれば、とりわけ６００℃付近における高温特性に優れた水素透過膜を得ることができる。また、Ｐｄは貴金属であり高価であるところ、本発明に係る水素透過膜の組成に占めるＰｄの割合は原子比でＣｕ以下であることから、従来に比べて安価に製造できるようになる。 According to the present invention, it is possible to obtain a hydrogen permeable membrane having excellent high temperature characteristics particularly at around 600 ° C. Moreover, since Pd is a noble metal and is expensive, the proportion of Pd in the composition of the hydrogen permeable membrane according to the present invention is Cu or less in atomic ratio, so that it can be manufactured at a lower cost than conventional.
以下、本発明の実施形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
本発明に係る銅合金は所定の原子比を満足するＣｕ、Ｐｄ及びＡｌの三成分で構成される。具体的には、本発明に係る銅合金はＣｕ、Ｐｄ及びＡｌの原子濃度（ａｔ％）をそれぞれ［Ｃｕ］、［Ｐｄ］及び［Ａｌ］とすると、［Ｐｄ］／（［Ｃｕ］＋［Ｐｄ］）＝４１〜５０％、［Ａｌ］／（［Ｃｕ］＋［Ｐｄ］）＝０．０５〜４．０％を満たす組成を有する。 The copper alloy according to the present invention is composed of three components of Cu, Pd and Al that satisfy a predetermined atomic ratio. Specifically, in the copper alloy according to the present invention, when the atomic concentrations (at%) of Cu, Pd and Al are [Cu], [Pd] and [Al], respectively, [Pd] / ([Cu] + [ Pd]) = 41 to 50% and [Al] / ([Cu] + [Pd]) = 0.05 to 4.0%.
本発明においては、原子濃度は、一定の質量の銅合金に含まれるＣｕのモル数、Ｐｄのモル数及びＡｌのモル数を求め、
［Ｃｕ］＝（Ｃｕのモル数）／（Ｃｕのモル数＋Ｐｄのモル数＋Ａｌのモル数）
［Ｐｄ］＝（Ｐｄのモル数）／（Ｃｕのモル数＋Ｐｄのモル数＋Ａｌのモル数）
［Ａｌ］＝（Ａｌのモル数）／（Ｃｕのモル数＋Ｐｄのモル数＋Ａｌのモル数）
で計算される。
In the present invention, the atomic concentration is determined by obtaining the number of moles of Cu, the number of moles of Pd and the number of moles of Al contained in a copper alloy having a constant mass,
[Cu] = (number of moles of Cu) / (number of moles of Cu + number of moles of Pd + number of moles of Al)
[Pd] = (number of moles of Pd) / (number of moles of Cu + number of moles of Pd + number of moles of Al)
[Al] = (number of moles of Al) / (number of moles of Cu + number of moles of Pd + number of moles of Al)
Calculated by
Ｃｕ−Ｐｄ合金に対してアルミニウム（Ａｌ）を少量添加すると、６００℃付近の高温下における水素透過率が向上するという効果があり、［Ａｌ］／（［Ｃｕ］＋［Ｐｄ］）が０．０５ａｔ％以上になるとその効果が有意に表れてくる。ただし、［Ａｌ］／（［Ｃｕ］＋［Ｐｄ］）が４．０ａｔ％を超えると今度は水素透過率の向上効果がほとんどなくなり、逆に悪化するケースもある。そこで、本発明では［Ａｌ］／（［Ｃｕ］＋［Ｐｄ］）は０．０５〜４．０ａｔ％と規定している。 When a small amount of aluminum (Al) is added to the Cu—Pd alloy, there is an effect that the hydrogen permeability at a high temperature around 600 ° C. is improved, and [Al] / ([Cu] + [Pd]) is 0. The effect appears significantly when it is over 05at%. However, when [Al] / ([Cu] + [Pd]) exceeds 4.0 at%, the effect of improving the hydrogen permeability is almost lost, and there is a case where it deteriorates. Therefore, in the present invention, [Al] / ([Cu] + [Pd]) is defined as 0.05 to 4.0 at%.
パラジウム（Ｐｄ）は、アルミニウム（Ａｌ）が存在しない系においては、［Ｐｄ］／（［Ｃｕ］＋［Ｐｄ］）が５０ａｔ％以上となる濃度に設定したほうが６００℃付近の高温下における水素透過率は向上する傾向にあるが、本発明者の検討結果によれば、アルミニウムを含む系においては、上記の４１〜５０ａｔ％の範囲が６００℃付近の高温下における高い水素透過率を得る観点で好ましく、５０ａｔ％を超えると逆に水素透過率が低下していく傾向にある。 Palladium (Pd) has a hydrogen permeation at a high temperature around 600 ° C. when [Pd] / ([Cu] + [Pd]) is set to a concentration of 50 at% or more in a system in which aluminum (Al) is not present. Although the rate tends to improve, according to the study results of the present inventors, in the system containing aluminum, the above 41 to 50 at% range is obtained from the viewpoint of obtaining a high hydrogen permeability at a high temperature around 600 ° C. Preferably, when it exceeds 50 at%, the hydrogen permeability tends to decrease.
パラジウムの濃度が高いときには６００℃付近の高温下における最も高い水素透過率を得ることのできるアルミニウム濃度は高い方へシフトする傾向にある。逆に、パラジウムの濃度が低いときには６００℃付近の高温下における最も高い水素透過率を得ることのできるアルミニウム濃度も低い方へシフトする傾向にある。そのため、［Ｐｄ］／（［Ｃｕ］＋［Ｐｄ］）が４７ａｔ％を超える範囲では［Ａｌ］／（［Ｃｕ］＋［Ｐｄ］）は１．５ａｔ％を超えることが好ましく、［Ｐｄ］／（［Ｃｕ］＋［Ｐｄ］）が４７％以下の範囲では［Ａｌ］／（［Ｃｕ］＋［Ｐｄ］）は１．５ａｔ％以下とすることが好ましい。６００℃付近で特に高い水素透過率を示すパラジウム濃度とアルミニウム濃度の組み合わせは、［Ｐｄ］／（［Ｃｕ］＋［Ｐｄ］）が４４〜４７ａｔ％、且つ、［Ａｌ］／（［Ｃｕ］＋［Ｐｄ］）が０．４〜１．５ａｔ％である。 When the concentration of palladium is high, the aluminum concentration at which the highest hydrogen permeability can be obtained at a high temperature around 600 ° C. tends to shift to a higher level. Conversely, when the palladium concentration is low, the aluminum concentration at which the highest hydrogen permeability at a high temperature around 600 ° C. tends to shift to the lower side. Therefore, in a range where [Pd] / ([Cu] + [Pd]) exceeds 47 at%, it is preferable that [Al] / ([Cu] + [Pd]) exceeds 1.5 at%, and [Pd] / In the range where ([Cu] + [Pd]) is 47% or less, [Al] / ([Cu] + [Pd]) is preferably 1.5 at% or less. The combination of palladium concentration and aluminum concentration exhibiting particularly high hydrogen permeability near 600 ° C. is [Pd] / ([Cu] + [Pd]) of 44 to 47 at% and [Al] / ([Cu] + [Pd]) is 0.4 to 1.5 at%.
同様に、パラジウムの濃度が高いときには所望の効果を発揮する上で許容されるアルミニウム濃度も高くなる傾向にあり、パラジウムの濃度が低いときには許容されるアルミニウム濃度も低くなる傾向にある。本発明者の検討結果によれば、６００℃付近の高温下において優れた水素透過率を得るためには、銅、パラジウム及びアルミニウムの原子比の関係として次式：
［Ａｌ］／（［Ｃｕ］＋［Ｐｄ］）≦（２／９）×［Ｐｄ］／（［Ｃｕ］＋［Ｐｄ］）−（０．６４／９）
を満たすことが必要である。
Similarly, when the concentration of palladium is high, the aluminum concentration allowed to exhibit a desired effect tends to be high, and when the concentration of palladium is low, the allowable aluminum concentration tends to be low. According to the study results of the present inventor, in order to obtain an excellent hydrogen permeability at a high temperature around 600 ° C., the relationship of the atomic ratio of copper, palladium and aluminum is as follows:
[Al] / ([Cu] + [Pd]) ≦ (2/9) × [Pd] / ([Cu] + [Pd]) − (0.64 / 9)
It is necessary to satisfy.
本発明に係る銅合金は、Ｃｕ、Ｐｄ及びＡｌの三成分で構成されており、他の元素を積極的に含有させることはないが、製造過程で混入する不可避的不純物のように他の元素が極微量含有していても構わないため、そのような場合も本発明の範囲とする。他の元素の許容値は一概には決定できないが、６００℃付近における水素透過係数に有意な悪影響を与えない程度の場合（例：水素透過係数の低下率が５％以下）、例えばＣｕ、Ｐｄ及びＡｌの合計に対してそれぞれ１ａｔ％以下の濃度で混入している場合には有意な悪影響はないと考えられる。他の元素としては、限定的ではないが、水素透過膜への添加元素として公知であるＧａ、Ｐｔ、Ｒｈ、Ｉｒ、Ｒｕ、Ｎｉ、Ｃｏ、Ｔｉ、Ｎｂ、Ｔａ、Ａｇ、Ｂ、Ｙ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ及びＬｕが挙げられる。 The copper alloy according to the present invention is composed of three components of Cu, Pd and Al, and does not actively contain other elements, but other elements such as inevitable impurities mixed in during the manufacturing process. However, such a case is also included in the scope of the present invention. The allowable values of other elements cannot be determined in general, but when the hydrogen permeation coefficient is not significantly adversely affected near 600 ° C. (eg, the rate of decrease of the hydrogen permeation coefficient is 5% or less), for example, Cu, Pd In addition, it is considered that there is no significant adverse effect when it is mixed at a concentration of 1 at% or less with respect to the total of Al and Al. Other elements include, but are not limited to, Ga, Pt, Rh, Ir, Ru, Ni, Co, Ti, Nb, Ta, Ag, B, Y, La, which are known as additive elements to the hydrogen permeable film. , Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
本発明に係る銅合金は、このようにＡｌを所定量添加したＣｕ−Ｐｄ合金であり、６００℃付近における水素透過率がＡｌを添加しない場合よりも有意に高い。このため、当該温度付近で水素含有ガスから水素を分離することが要求される場合に用いる水素透過膜として特に好適に使用できる。 The copper alloy according to the present invention is a Cu—Pd alloy to which a predetermined amount of Al is added as described above, and the hydrogen permeability in the vicinity of 600 ° C. is significantly higher than that in the case of not adding Al. For this reason, it can be particularly suitably used as a hydrogen permeable membrane used when it is required to separate hydrogen from a hydrogen-containing gas near the temperature.
本発明に係る銅合金は、限定されるものではないが、所定の成分に調整したインゴットを溶解鋳造した後、適宜焼鈍及び圧延を繰り返すことで製造可能である。具体的には、８００℃以上で加熱したインゴットを熱間圧延し、黒皮除去後、冷間圧延で所定厚みまで薄くする。必要に応じて焼鈍を行う。また、湿式めっきやスパッタリングで作製することも可能である。 Although the copper alloy which concerns on this invention is not limited, after melt-casting the ingot adjusted to the predetermined component, it can manufacture by repeating annealing and rolling suitably. Specifically, an ingot heated at 800 ° C. or higher is hot-rolled, and after removing the black skin, it is thinned to a predetermined thickness by cold rolling. Annealing is performed as necessary. It can also be produced by wet plating or sputtering.
本発明に係る銅合金を水素透過膜として利用する場合、水素透過量は膜厚に反比例するため、膜厚が薄いほど単位面積当たりの透過量は上昇する。また、同じ面積でも膜厚が薄いと使用する材料も少なくなることから、膜厚を薄くすることは水素透過膜として使用する場合、非常に効果的である。ただし、あまり薄すぎると機械的強度が保てず、ピンホール等によって水素以外の不純物ガスが二次側に到達してしまうことから一定以上の膜厚があることが必要である。一方、膜厚があまり厚すぎると今度は二次側に到達する水素の量が少なくなり、生産性が悪くなる。そこで、膜厚は１〜２００μｍとするのが好ましく、３〜１００μｍとするのがより好ましい。膜厚は圧延時の圧下率を制御することで調節可能である。 When the copper alloy according to the present invention is used as a hydrogen permeable membrane, the hydrogen permeation amount is inversely proportional to the film thickness, so that the permeation amount per unit area increases as the film thickness decreases. Moreover, since the material to be used is reduced when the film thickness is small even in the same area, it is very effective to reduce the film thickness when used as a hydrogen permeable film. However, if it is too thin, the mechanical strength cannot be maintained, and an impurity gas other than hydrogen reaches the secondary side due to pinholes or the like, so that it is necessary to have a certain thickness or more. On the other hand, if the film thickness is too thick, the amount of hydrogen that reaches the secondary side is reduced and productivity is deteriorated. Therefore, the film thickness is preferably 1 to 200 μm, and more preferably 3 to 100 μm. The film thickness can be adjusted by controlling the rolling reduction during rolling.
本発明に係る水素透過膜を利用して水素含有ガスから水素を分離する方法は、水素含有ガスが当該水素透過膜を通過する工程を含む。一般的には、膜の一方の面（一次側）に水素を含有する混合ガスを配置し、一次側の圧力を膜の他方の面（二次側）に対して高くする方法が採用される。本発明に係る水素透過膜は特に６００℃付近での水素透過率に優れていることから、水素含有ガスは５５０〜６５０℃の温度として水素透過膜を通過することが好ましく、５８０〜６２０℃の温度として水素透過膜を通過することがより好ましい。 The method for separating hydrogen from a hydrogen-containing gas using the hydrogen-permeable membrane according to the present invention includes a step of passing the hydrogen-containing gas through the hydrogen-permeable membrane. Generally, a method is adopted in which a mixed gas containing hydrogen is disposed on one side (primary side) of the membrane, and the pressure on the primary side is increased relative to the other side (secondary side) of the membrane. . Since the hydrogen permeable membrane according to the present invention is particularly excellent in hydrogen permeability at around 600 ° C., the hydrogen-containing gas preferably passes through the hydrogen permeable membrane at a temperature of 550 to 650 ° C. More preferably, the temperature passes through the hydrogen permeable membrane.
水素透過膜を利用して水素含有ガスから水素を分離するシステム自体は公知であり、任意の公知のシステムを採用することができ、特に制限はない。一例を挙げると、本発明に係る水素分離システムは水素含有ガスを流すための一次側配管と、水素透過膜をガス通路に設置した加熱管と、水素透過膜を通過した後の水素ガスを流すための二次側配管とを備え、加熱管の入口を一次側配管に、出口を二次側配管に連結したシステムである。別の一例を挙げると、本発明に係る水素透過膜は水素分離型改質器であるメンブレンリフォーマーに組み込む水素透過膜として使用することができる。 A system itself for separating hydrogen from a hydrogen-containing gas using a hydrogen permeable membrane is known, and any known system can be adopted without any particular limitation. For example, the hydrogen separation system according to the present invention is configured to flow a primary side pipe for flowing a hydrogen-containing gas, a heating pipe having a hydrogen permeable membrane installed in a gas passage, and a hydrogen gas after passing through the hydrogen permeable membrane. And a secondary side pipe for connecting the inlet of the heating pipe to the primary side pipe and the outlet to the secondary side pipe. As another example, the hydrogen permeable membrane according to the present invention can be used as a hydrogen permeable membrane incorporated in a membrane reformer which is a hydrogen separation type reformer.
以下に本発明を実施例でさらに詳細に説明するが、本発明はこれらに限定されるものではない。 The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.
＜１．合金組成が与える影響＞
Ｃｕ、Ｐｄ及びＡｌで構成され、表１に記載の原子比を満足する組成となるように成分調整したＣｕ−Ｐｄ−Ａｌ合金をそれぞれ溶解鋳造後、８００℃以上に加熱したインゴットを熱間圧延し、黒皮除去後、膜厚２５μｍの膜に冷間圧延した。
膜厚はマイクロメータで測定した５箇所の平均値を指す。
<1. Effect of alloy composition>
An ingot heated at 800 ° C. or higher after hot casting each Cu—Pd—Al alloy composed of Cu, Pd, and Al and adjusted to have a composition satisfying the atomic ratio shown in Table 1 was hot-rolled. After removing the black skin, the film was cold-rolled to a film thickness of 25 μm.
The film thickness refers to the average value of five locations measured with a micrometer.
このようにして得られたそれぞれの膜に対して、以下の要領で水素透過係数を測定した。
水素のガスボンベ（図示せず）、加熱炉１１、一次側水素配管１２、二次側水素配管１３、管状炉内に配置され、一次側水素配管及び二次側水素配管を連結する１／２ＶＣＲ（登録商標）継手内にガスケットと共に固定された水素透過膜１４（水素透過部の直径１１．２ｍｍ）、二次側の水素配管に連結した水素測定器（水素用マスフローコントローラ（山武、ＭＱＶ９０５０））１５を備えた測定系を構築した（図１参照）。水素のガスボンベから配管を通じて供給される水素はＶＣＲ継手の一次側に入り、水素透過膜を通過して、ＶＣＲ継手の二次側から出てくる。水素透過膜を固定したＶＣＲ継手が入っている管状炉は所定の温度に加熱可能となっており、水素固定部のＶＣＲ継手部分の温度を熱電対で測定している。測定試験は、一次側圧を０．１ＭＰａＧ、二次側圧を０ＭＰａＧとし、一次側の水素供給量を２０ｓｃｃｍとして６００℃に水素を加熱しながら３時間供給し続けたときの水素透過量を測定し、以下の式により水素透過係数ｑを測定した。
ｑ＝ｆM・ｄ・Ｓ-1・（Ｐ1/2−ｐ1/2）-1
ｑ：水素透過係数（ｍｏｌ・ｍ-1・ｓｅｃ-1・Ｐａ-1/2）
ｆM：二次側水素流量（ｍｏｌ・ｓｅｃ-1）
ｄ：膜厚（ｍ）
Ｓ：膜面積（ｍ2）
Ｐ：一次側圧力（Ｐａ）
ｐ：二次側圧力（Ｐａ）
The hydrogen permeation coefficient was measured for each of the membranes thus obtained in the following manner.
A hydrogen gas cylinder (not shown), a heating furnace 11, a primary-side hydrogen pipe 12, a secondary-side hydrogen pipe 13, and a 1/2 VCR that is arranged in a tubular furnace and connects the primary-side hydrogen pipe and the secondary-side hydrogen pipe ( (Registered trademark) Hydrogen permeable membrane 14 (hydrogen permeable part diameter 11.2 mm) fixed with a gasket in the joint, hydrogen measuring instrument (hydrogen mass flow controller (Yamatake, MQV9050)) 15 connected to the secondary side hydrogen piping 15 Was constructed (see FIG. 1). Hydrogen supplied through a pipe from a hydrogen gas cylinder enters the primary side of the VCR joint, passes through the hydrogen permeable membrane, and exits from the secondary side of the VCR joint. The tubular furnace containing the VCR joint to which the hydrogen permeable membrane is fixed can be heated to a predetermined temperature, and the temperature of the VCR joint portion of the hydrogen fixing portion is measured with a thermocouple. In the measurement test, the primary side pressure was set to 0.1 MPaG, the secondary side pressure was set to 0 MPaG, the primary side hydrogen supply amount was set to 20 sccm, and the hydrogen permeation amount was measured while continuing to supply hydrogen at 600 ° C. for 3 hours, The hydrogen permeation coefficient q was measured by the following formula.
q = f M · d · S -1 · (P 1/2 -p 1/2) -1
q: Hydrogen permeation coefficient (mol · m -1 · sec -1 · Pa -1/2 )
f M : secondary hydrogen flow rate (mol · sec −1 )
d: Film thickness (m)
S: membrane area (m 2 )
P: Primary pressure (Pa)
p: Secondary pressure (Pa)
試験結果を表１に示す。図２は、横軸に［Ｐｄ］／（［Ｃｕ］＋［Ｐｄ］）（以下、「Ｐｄ比」ともいう）、縦軸に［Ａｌ］／（［Ｃｕ］＋［Ｐｄ］）（以下、「Ａｌ比」ともいう）をとり、試験したデータ範囲を示している。台形で囲った範囲が本発明の範囲である。得られた結果を幾つかの切り口で以下に検討してみる。
（１）［Ｐｄ］／（［Ｃｕ］＋［Ｐｄ］）：約４１ａｔ％
表１からＰｄ比が４１ａｔ％付近の例を抽出し、Ａｌ比の小さい順に並べたのが表２である。表２より、Ａｌ比が０のとき（Ｎｏ．１）は水素透過係数が最も低く、Ａｌ比が増加するにつれて水素透過係数が徐々に上昇し、Ａｌ比が０．４９ａｔ％のとき（Ｎｏ．４）に最大の水素透過係数が得られた。その後、更にＡｌ比を増加させていくと今度は徐々に水素透過率が減少していき、Ａｌ比が２．３０まで増えると（Ｎｏ．２１）、式：［Ａｌ］／（［Ｃｕ］＋［Ｐｄ］）≦（２／９）×［Ｐｄ］／（［Ｃｕ］＋［Ｐｄ］）−（０．６４／９）を満たさなくなったため、優れた水素透過係数は得られなくなった。
(1) [Pd] / ([Cu] + [Pd]): about 41 at%
Table 2 shows an example in which the Pd ratio is around 41 at% extracted from Table 1 and arranged in order of increasing Al ratio. From Table 2, when the Al ratio is 0 (No. 1), the hydrogen permeation coefficient is the lowest, the hydrogen permeation coefficient gradually increases as the Al ratio increases, and when the Al ratio is 0.49 at% (No. 1). The maximum hydrogen permeation coefficient was obtained in 4). Thereafter, when the Al ratio is further increased, the hydrogen permeability gradually decreases. When the Al ratio increases to 2.30 (No. 21), the formula: [Al] / ([Cu] + Since [Pd]) ≦ (2/9) × [Pd] / ([Cu] + [Pd]) − (0.64 / 9) was not satisfied, an excellent hydrogen permeability coefficient could not be obtained.
（２）［Ｐｄ］／（［Ｃｕ］＋［Ｐｄ］）：約４６ａｔ％
表１からＰｄ比が４６ａｔ％付近の例を抽出し、Ａｌ比の小さい順に並べたのが表３である。表３より、Ａｌ比が０のとき（Ｎｏ．６）は水素透過係数が最も低く、Ａｌ比が増加するにつれて水素透過係数が徐々に上昇し、Ａｌ比が０．９９ａｔ％のとき（Ｎｏ．９）に最大の水素透過係数が得られた。その後、更にＡｌ比を増加させていくと今度は徐々に水素透過率が減少していき、Ａｌ比が３．２７まで増えると（Ｎｏ．２２）、式：［Ａｌ］／（［Ｃｕ］＋［Ｐｄ］）≦（２／９）×［Ｐｄ］／（［Ｃｕ］＋［Ｐｄ］）−（０．６４／９）を満たさなくなったため、優れた水素透過係数は得られなくなった。
(2) [Pd] / ([Cu] + [Pd]): about 46 at%
Table 3 shows an example in which the Pd ratio is around 46 at% extracted from Table 1 and arranged in ascending order of the Al ratio. From Table 3, when the Al ratio is 0 (No. 6), the hydrogen permeation coefficient is the lowest, the hydrogen permeation coefficient gradually increases as the Al ratio increases, and when the Al ratio is 0.99 at% (No. 6). The maximum hydrogen permeation coefficient was obtained in 9). Thereafter, when the Al ratio is further increased, the hydrogen permeability gradually decreases. When the Al ratio increases to 3.27 (No. 22), the formula: [Al] / ([Cu] + Since [Pd]) ≦ (2/9) × [Pd] / ([Cu] + [Pd]) − (0.64 / 9) was not satisfied, an excellent hydrogen permeability coefficient could not be obtained.
（３）［Ｐｄ］／（［Ｃｕ］＋［Ｐｄ］）：約５０ａｔ％
表１からＰｄ比が５０ａｔ％付近の例を抽出し、Ａｌ比の小さい順に並べたのが表４である。表４より、Ａｌ比が０のとき（Ｎｏ．１２）は水素透過係数が最も低く、Ａｌ比が増加するにつれて水素透過係数が徐々に上昇し、Ａｌ比が１．９６ａｔ％のとき（Ｎｏ．１６）に最大の水素透過係数が得られた。その後、更にＡｌ比を増加させていくと今度は徐々に水素透過率が減少していき、Ａｌ比が４．２５まで増えると（Ｎｏ．２３）、式：［Ａｌ］／（［Ｃｕ］＋［Ｐｄ］）≦（２／９）×［Ｐｄ］／（［Ｃｕ］＋［Ｐｄ］）−（０．６４／９）を満たさなくなったため、優れた水素透過係数は得られなくなった。
(3) [Pd] / ([Cu] + [Pd]): about 50 at%
Table 4 shows an example in which the Pd ratio is around 50 at% extracted from Table 1 and arranged in ascending order of Al ratio. From Table 4, when the Al ratio is 0 (No. 12), the hydrogen permeation coefficient is the lowest, the hydrogen permeation coefficient gradually increases as the Al ratio increases, and when the Al ratio is 1.96 at% (No. 12). The maximum hydrogen permeation coefficient was obtained in 16). Thereafter, when the Al ratio is further increased, the hydrogen permeability gradually decreases. When the Al ratio increases to 4.25 (No. 23), the formula: [Al] / ([Cu] + Since [Pd]) ≦ (2/9) × [Pd] / ([Cu] + [Pd]) − (0.64 / 9) was not satisfied, an excellent hydrogen permeability coefficient could not be obtained.
上記の（１）、（２）及び（３）について、横軸をＡｌ比とし、縦軸を水素透過係数としてプロットしたものが図３である。 FIG. 3 is a plot of the above (1), (2) and (3) plotted with the horizontal axis as the Al ratio and the vertical axis as the hydrogen permeation coefficient.
（４）［Ａｌ］／（［Ｃｕ］＋［Ｐｄ］）：０ａｔ％
表１からＡｌ比が０ａｔ％の例を抽出し、Ｐｄ比の小さい順に並べたのが表５である。表５より、Ｐｄ比が４１．３ａｔ％のとき（Ｎｏ．１）は水素透過係数が最も低く、Ｐｄ比が増加するにつれて水素透過係数が徐々に上昇し、Ｐｄ比が５０．２ａｔ％のとき（Ｎｏ．１２）に最大の水素透過係数が得られた。ただし、Ａｌ比が０ａｔ％であったため、本発明に匹敵する水素透過係数は得られなかった。
(4) [Al] / ([Cu] + [Pd]): 0 at%
Table 5 shows an example in which the Al ratio is 0 at% extracted from Table 1 and arranged in ascending order of the Pd ratio. From Table 5, when the Pd ratio is 41.3 at% (No. 1), the hydrogen permeation coefficient is the lowest, and as the Pd ratio increases, the hydrogen permeation coefficient gradually increases, and when the Pd ratio is 50.2 at%. The maximum hydrogen permeation coefficient was obtained for (No. 12). However, since the Al ratio was 0 at%, a hydrogen permeation coefficient comparable to the present invention was not obtained.
（５）［Ａｌ］／（［Ｃｕ］＋［Ｐｄ］）：０．５ａｔ％
表１からＡｌ比が約０．５ａｔ％の例を抽出し、Ｐｄ比の小さい順に並べたのが表６である。表６より、Ｐｄ比が３９．１ａｔ％のとき（Ｎｏ．２４）は水素透過係数が最も低く、Ｐｄ比が増加するにつれて水素透過係数が徐々に上昇し、Ｐｄ比が４６．０ａｔ％のとき（Ｎｏ．８）に最大の水素透過係数が得られた。その後、更にＰｄ比を増加させていくと今度は徐々に水素透過率が減少していき、Ｐｄ比が５１．９ａｔ％まで増えると（Ｎｏ．２５）、優れた水素透過係数は得られなくなった。
(5) [Al] / ([Cu] + [Pd]): 0.5 at%
Table 6 shows an example in which the Al ratio is about 0.5 at% extracted from Table 1 and arranged in ascending order of the Pd ratio. From Table 6, when the Pd ratio is 39.1 at% (No. 24), the hydrogen permeation coefficient is the lowest, and as the Pd ratio increases, the hydrogen permeation coefficient gradually increases, and when the Pd ratio is 46.0 at%. The maximum hydrogen permeation coefficient was obtained for (No. 8). Thereafter, when the Pd ratio is further increased, the hydrogen permeability is gradually reduced. When the Pd ratio is increased to 51.9 at% (No. 25), an excellent hydrogen permeability coefficient cannot be obtained. .
（６）［Ａｌ］／（［Ｃｕ］＋［Ｐｄ］）：２．０ａｔ％
表１からＡｌ比が約２．０ａｔ％の例を抽出し、Ｐｄ比の小さい順に並べたのが表７である。表７より、Ｐｄ比が３９．４ａｔ％のとき（Ｎｏ．２６）は水素透過係数が最も低く、Ｐｄ比が増加するにつれて水素透過係数が徐々に上昇し、Ｐｄ比が４９．５ａｔ％のとき（Ｎｏ．１６）に最大の水素透過係数が得られた。その後、更にＰｄ比を増加させていくと今度は徐々に水素透過率が減少していき、Ｐｄ比が５２．４ａｔ％まで増えると（Ｎｏ．２７）、優れた水素透過係数は得られなくなった。
(6) [Al] / ([Cu] + [Pd]): 2.0 at%
Table 7 shows an example in which the Al ratio is about 2.0 at% extracted from Table 1 and arranged in ascending order of the Pd ratio. From Table 7, when the Pd ratio is 39.4 at% (No. 26), the hydrogen permeation coefficient is the lowest, and as the Pd ratio increases, the hydrogen permeation coefficient gradually increases, and when the Pd ratio is 49.5 at%. The maximum hydrogen permeation coefficient was obtained for (No. 16). Thereafter, when the Pd ratio is further increased, the hydrogen permeability gradually decreases. When the Pd ratio increases to 52.4 at% (No. 27), an excellent hydrogen permeability coefficient cannot be obtained. .
上記の（４）、（５）及び（６）について、横軸をＰｄ比とし、縦軸を水素透過係数としてプロットしたものが図４である。 FIG. 4 is a plot of the above (4), (5), and (6) plotted with the horizontal axis as the Pd ratio and the vertical axis as the hydrogen permeation coefficient.
＜２．加熱温度の影響＞
Ｃｕ、Ｐｄ及びＡｌで構成され、表８に記載の原子比を満足する組成となるように成分調整したＣｕ−Ｐｄ−Ａｌ合金をそれぞれ溶解鋳造後、８００℃以上に加熱したインゴットを熱間圧延し、黒皮除去後、膜厚２５μｍの膜に冷間圧延した。
<2. Effect of heating temperature>
An ingot heated at 800 ° C. or higher after hot casting each Cu—Pd—Al alloy composed of Cu, Pd, and Al and adjusted to have a composition satisfying the atomic ratio shown in Table 8 was hot-rolled. After removing the black skin, the film was cold-rolled to a film thickness of 25 μm.
このようにして得られたそれぞれの膜に対して、先の実施例と同様の手順で水素透過係数を測定した。ただし、水素ガスの加熱温度を３５０℃、４００℃、４５０℃、５００℃、及び６００℃に変動させることで、水素透過係数の変化を調べた。 For each of the membranes thus obtained, the hydrogen permeation coefficient was measured in the same procedure as in the previous example. However, the change of the hydrogen permeability coefficient was investigated by changing the heating temperature of the hydrogen gas to 350 ° C., 400 ° C., 450 ° C., 500 ° C., and 600 ° C.
試験結果を、温度（℃）を横軸に、水素透過係数を縦軸にしてプロットして示したのが図５である。これらから、Ｃｕ−Ｐｄ合金に対してＡｌを所定量添加した場合、水素透過係数は、低温領域ではＡｌを添加しない場合よりも低いにもかかわらず、高温条件下（とりわけ６００℃付近）では逆転し、Ａｌを添加しない場合よりも高いことが分かる。
Claims (6)
の関係を満たす水素透過性銅合金。 It is a hydrogen permeable copper alloy composed of Cu, Pd and Al. When the atomic concentrations (at%) of Cu, Pd and Al are [Cu], [Pd] and [Al], respectively, [Pd] / ( [Cu] + [Pd]) = 41-50%, [Al] / ([Cu] + [Pd]) = 0.05-4.0%, and the formula: [Al] / ([Cu] + [Pd]) ≦ (2/9) × [Pd] / ([Cu] + [Pd]) − (0.64 / 9)
Hydrogen permeable copper alloy that satisfies the relationship
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