JP2020142197A - Hydrogen permeation apparatus and method for manufacturing hydrogen permeation apparatus - Google Patents
Hydrogen permeation apparatus and method for manufacturing hydrogen permeation apparatus Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 249
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- 238000012360 testing method Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 20
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- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
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- 239000002131 composite material Substances 0.000 description 39
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- 230000008859 change Effects 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 10
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
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- 239000012466 permeate Substances 0.000 description 4
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
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- 239000006104 solid solution Substances 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 239000011733 molybdenum Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- 239000011593 sulfur Substances 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
本開示は、水素透過装置及びその製造方法に関する。 The present disclosure relates to a hydrogen permeation device and a method for producing the same.
近年、水素が様々な分野において注目され、重要な役割を果たしている。例えば、家庭用燃料電池型コージェネレーションシステムや燃料電池自動車などにおいて、新しいエネルギーとして水素が利用されている。また、気相エピタキシャル成長法を用いたＳｉウェハ半導体材料の結晶成長や加工におけるキャリアガスとして、高純度水素ガスが使用されている。 In recent years, hydrogen has attracted attention in various fields and plays an important role. For example, hydrogen is used as a new energy in household fuel cell type cogeneration systems and fuel cell vehicles. Further, high-purity hydrogen gas is used as a carrier gas in crystal growth and processing of a Si wafer semiconductor material using a vapor phase epitaxial growth method.
固体高分子型燃料電池では、一酸化炭素等の不純物ガスによって負極触媒が被毒されるため、高純度の水素ガスを使用することが求められる。例えば、燃料電池自動車では、総合純度が９９．９７％以上の高純度水素を供給する必要がある上、硫黄成分が４ｐｐｂ以下、ホルムアルデヒドが１０ｐｐｂ以下、ハロゲンが５０ｐｐｂ以下などの厳しい規制がある。また、半導体材料の結晶成長や加工におけるキャリアガスとして水素を使用する場合、不純物の混入によって半導体特性が低下することを避けるため、９９．９９９９９９９％以上の超高純度水素ガスが必要とされる。さらに、アンモニアやメタノール等の薬品を製造する原料としても、高純度水素が必要とされている。なお、副生水素や水素キャリアからの分解ガスなど水素以外の気体成分を含む水素混合ガスからも高純度の水素ガスを分離回収する技術が要求されている。このように、高純度の水素の需要が益々高まっているため、高純度の水素を高効率かつ安定的に供給する技術が求められている。 In polymer electrolyte fuel cells, the negative electrode catalyst is poisoned by impurity gas such as carbon monoxide, so it is required to use high-purity hydrogen gas. For example, in a fuel cell vehicle, it is necessary to supply high-purity hydrogen having a total purity of 99.97% or more, and there are strict regulations such as sulfur component of 4 ppb or less, formaldehyde of 10 ppb or less, and halogen of 50 ppb or less. Further, when hydrogen is used as a carrier gas in crystal growth or processing of a semiconductor material, an ultra-high purity hydrogen gas of 99.999999999% or more is required in order to avoid deterioration of semiconductor characteristics due to mixing of impurities. Further, high-purity hydrogen is required as a raw material for producing chemicals such as ammonia and methanol. There is also a demand for a technique for separating and recovering high-purity hydrogen gas from a hydrogen mixed gas containing a gas component other than hydrogen, such as by-product hydrogen and decomposition gas from a hydrogen carrier. As described above, the demand for high-purity hydrogen is increasing more and more, and therefore, a technique for supplying high-purity hydrogen with high efficiency and stability is required.
水素を含む原料気体から水素を分離する技術として、本発明者らによる特許文献１がある。本発明者らは、特許文献１に記載された発明を更に改良し、本開示の技術に想到した。 Patent Document 1 by the present inventors is a technique for separating hydrogen from a raw material gas containing hydrogen. The present inventors further improved the invention described in Patent Document 1 and came up with the technique of the present disclosure.
本開示は、このような課題に鑑みてなされ、その目的は、水素透過装置の性能を向上させることである。 The present disclosure is made in view of such a problem, and an object thereof is to improve the performance of a hydrogen permeation device.
上記課題を解決するために、本発明のある態様の水素透過装置は、純金属又は合金により形成された水素透過膜と、水素透過膜の表面に設けられた触媒層と、を備える。触媒層との境界面における水素透過膜の金属又は合金の所定比率以上が特定の結晶方位に配向する。 In order to solve the above problems, the hydrogen permeation device according to an embodiment of the present invention includes a hydrogen permeation membrane formed of a pure metal or an alloy, and a catalyst layer provided on the surface of the hydrogen permeation membrane. A predetermined ratio or more of the metal or alloy of the hydrogen permeable membrane at the interface with the catalyst layer is oriented in a specific crystal orientation.
本発明のさらに別の態様もまた、水素透過装置である。この装置は、純金属又は合金により形成された水素透過膜と、水素透過膜の表面に設けられた触媒層と、を備える。触媒層との境界面における水素透過膜の金属又は合金は、（１１０）面に配向した領域がその他の面に配向した領域よりも大きい。 Yet another aspect of the present invention is also a hydrogen permeation device. This device includes a hydrogen permeable membrane formed of a pure metal or alloy, and a catalyst layer provided on the surface of the hydrogen permeable membrane. The metal or alloy of the hydrogen permeable membrane at the interface with the catalyst layer has a region oriented to the (110) plane larger than a region oriented to the other plane.
本発明のさらに別の態様もまた、水素透過装置である。この装置は、純金属又は合金により形成された水素透過膜と、水素透過膜の表面にパラジウムと銀の合金により形成された触媒層と、を備える。触媒層におけるパラジウムと銀の組成比は、一次側圧力が４００ｋＰａ、二次側圧力が１０３ｋＰａ、温度が４５０℃の条件下で水素透過膜の水素透過試験を実施した場合に透過流速が開始直後の透過流速から２０％減少する時点までの時間である２０％劣化時間ｔ０．２が４０時間以上となるような組成比である。 Yet another aspect of the present invention is also a hydrogen permeation device. The apparatus comprises a hydrogen permeable membrane formed of a pure metal or alloy and a catalyst layer formed of an alloy of palladium and silver on the surface of the hydrogen permeable membrane. The composition ratio of palladium and silver in the catalyst layer is such that when the hydrogen permeation test of the hydrogen permeation film is carried out under the conditions of a primary pressure of 400 kPa, a secondary pressure of 103 kPa and a temperature of 450 ° C., the permeation flow velocity is immediately after the start. The composition ratio is such that the 20% deterioration time t 0.2, which is the time from the permeation flow velocity to the point of decrease by 20%, is 40 hours or more.
本発明のさらに別の態様は、水素透過装置の製造方法である。この方法は、純金属又は合金により水素透過膜を形成するステップと、水素透過膜の表面の純金属又は合金のうち特定の結晶方位に配向した領域を増加させるステップと、を備える。 Yet another aspect of the present invention is a method of manufacturing a hydrogen permeation device. The method comprises forming a hydrogen permeable membrane from a pure metal or alloy and increasing the region of the pure metal or alloy on the surface of the hydrogen permeable membrane that is oriented in a particular crystal orientation.
本開示によれば、水素透過装置の性能を向上させることができる。 According to the present disclosure, the performance of the hydrogen permeation device can be improved.
本開示の実施の形態として、非パラジウム（Ｐｄ）系金属、例えば、５族元素であるバナジウム（Ｖ）、ニオブ（Ｎｂ）、タンタル（Ｔａ）や、非Ｐｄ系金属を主たる金属とする合金（以下、単に「非Ｐｄ系合金」ともいう）により形成された水素透過膜を利用した水素分離装置について説明する。水素分離装置は、本開示に係る水素透過装置の一例であり、水素透過膜が水素を選択的に透過する性質を利用して、水素を含む流体から水素を分離する。まず、実施の形態に係る水素分離装置の概要について説明し、つづいて、本開示に係る水素透過装置及びその製造方法について説明する。 As an embodiment of the present disclosure, a non-palladium (Pd) -based metal, for example, a group 5 element vanadium (V), niobium (Nb), tantalum (Ta), or an alloy containing a non-Pd-based metal as a main metal ( Hereinafter, a hydrogen separation apparatus using a hydrogen permeable film formed of (also simply referred to as “non-Pd-based alloy”) will be described. The hydrogen separation device is an example of the hydrogen permeation device according to the present disclosure, and separates hydrogen from a fluid containing hydrogen by utilizing the property that the hydrogen permeation membrane selectively permeates hydrogen. First, the outline of the hydrogen separation device according to the embodiment will be described, and then the hydrogen permeation device and the manufacturing method thereof according to the present disclosure will be described.
［水素分離装置の構成］
図１は、実施の形態に係る水素分離装置の構成を示す。本図は、水素分離装置１０の断面を概略的に示す。水素分離装置１０は、水素を選択的に透過する非Ｐｄ系金属又は非Ｐｄ系合金により形成された水素透過膜５０と、水素を含む原料気体を水素透過膜５０の一次側の表面に供給するための原料気体供給流路２６と水素透過膜５０を透過しなかった原料気体を排出するための原料気体排出流路２８とが形成された一次側配管２０と、水素透過膜５０の二次側の表面へ透過した水素を回収するための水素回収流路３２が形成された二次側配管３０と、水素透過膜５０を一次側配管２０と二次側配管３０との間に気密に挟持するための一次側ガスケット４０及び二次側ガスケット４２とを備える。一次側配管２０は、同軸に配置された外管２２と内管２４の二重構造になっており、内管２４の内側が原料気体供給流路２６として機能し、外管２２と内管２４の間が原料気体排出流路２８として機能する。なお、気体の流れは逆であってもよい。
[Structure of hydrogen separator]
FIG. 1 shows the configuration of the hydrogen separation device according to the embodiment. This figure schematically shows a cross section of the hydrogen separator 10. The hydrogen separation device 10 supplies a hydrogen permeable film 50 formed of a non-Pd-based metal or a non-Pd-based alloy that selectively permeates hydrogen and a raw material gas containing hydrogen to the surface on the primary side of the hydrogen permeable film 50. The primary side pipe 20 in which the raw material gas supply flow path 26 for the purpose and the raw material gas discharge flow path 28 for discharging the raw material gas that did not permeate the hydrogen permeable film 50 are formed, and the secondary side of the hydrogen permeable film 50. The secondary side pipe 30 in which the hydrogen recovery flow path 32 for recovering the hydrogen permeated to the surface of the gas is formed, and the hydrogen permeation film 50 are airtightly sandwiched between the primary side pipe 20 and the secondary side pipe 30. A primary side gasket 40 and a secondary side gasket 42 for the purpose are provided. The primary side pipe 20 has a double structure of an outer pipe 22 and an inner pipe 24 arranged coaxially, and the inside of the inner pipe 24 functions as a raw material gas supply flow path 26, and the outer pipe 22 and the inner pipe 24 The space between them functions as a raw material gas discharge flow path 28. The gas flow may be reversed.
一次側配管２０の原料気体排出流路２８の内径も、二次側配管３０の水素回収流路３２の内径も、水素透過膜５０から遠い部分においては、一次側ガスケット４０及び二次側ガスケット４２の内径より細くされているが、一次側配管２０と二次側配管３０が水素透過膜５０を介して接続される開口部分においては、一次側ガスケット４０及び二次側ガスケット４２の内径と同じ内径まで拡張されている。すなわち、一次側配管２０の開口にも、二次側配管３０の開口にも、一次側ガスケット４０及び二次側ガスケット４２の内径と同じ内径を有する凹部が形成されている。これにより、水素透過膜５０の全体を効率良く利用して水素を分離することができる。 Both the inner diameter of the raw material gas discharge flow path 28 of the primary side pipe 20 and the inner diameter of the hydrogen recovery flow path 32 of the secondary side pipe 30 are the primary side gasket 40 and the secondary side gasket 42 in the portion far from the hydrogen permeation film 50. The inner diameter is the same as the inner diameter of the primary side gasket 40 and the secondary side gasket 42 at the opening where the primary side pipe 20 and the secondary side pipe 30 are connected via the hydrogen permeable film 50. Has been extended to. That is, both the opening of the primary side pipe 20 and the opening of the secondary side pipe 30 are formed with recesses having the same inner diameter as the inner diameters of the primary side gasket 40 and the secondary side gasket 42. As a result, hydrogen can be separated by efficiently utilizing the entire hydrogen permeation membrane 50.
原料気体供給流路２６は、図示しないレギュレーターを介して、水素を含む原料気体を生成する気体発生装置又は水素を含む原料気体を貯蔵する貯蔵タンクなどに接続される。水素を含む原料気体は、レギュレーターにより所定の圧力に調整されて、原料気体供給流路２６から水素透過膜５０の一次側の表面に供給される。水素回収流路３２は、水素透過膜５０を透過して水素回収流路３２に到達した水素を回収するための構成に接続される。 The raw material gas supply flow path 26 is connected to a gas generator that generates a raw material gas containing hydrogen, a storage tank that stores the raw material gas containing hydrogen, or the like via a regulator (not shown). The raw material gas containing hydrogen is adjusted to a predetermined pressure by a regulator and supplied from the raw material gas supply flow path 26 to the surface on the primary side of the hydrogen permeation membrane 50. The hydrogen recovery flow path 32 is connected to a configuration for recovering hydrogen that has passed through the hydrogen permeation membrane 50 and reached the hydrogen recovery flow path 32.
水素透過膜５０は、５族元素であるＶ、Ｎｂ、Ｔａの純金属、又は、５族元素に鉄（Ｆｅ）やニッケル（Ｎｉ）などの元素が添加された合金により形成される。従来、Ｐｄ又はＰｄの合金により形成されたＰｄ系の水素透過膜の研究開発が広く行われてきたが、Ｐｄは希少かつ高価な金属であることに加えて、水素透過能が不十分であることから、本発明者らは、その代替材料として、５族元素などの非Ｐｄ系金属又は非Ｐｄ系合金により形成された水素透過膜の設計開発を行ってきた。 The hydrogen permeable film 50 is formed of a pure metal of Group 5 elements V, Nb, and Ta, or an alloy in which an element such as iron (Fe) or nickel (Ni) is added to the Group 5 element. Conventionally, research and development of a Pd-based hydrogen permeable film formed of Pd or an alloy of Pd has been widely carried out, but Pd is a rare and expensive metal and has insufficient hydrogen permeability. Therefore, the present inventors have been designing and developing a hydrogen permeable film formed of a non-Pd-based metal such as a Group 5 element or a non-Pd-based alloy as an alternative material.
面心立方（ｆｃｃ）格子構造をもつＰｄに比べて、体心立方（ｂｃｃ）格子構造をもつＶ、Ｎｂ、Ｔａは、水素の拡散の活性化エネルギーが小さいため、低温における水素の拡散係数が大きいという特徴がある。したがって、これらの金属又は合金により形成された水素透過膜を使用することにより、比較的低温においても高い水素透過速度が得られると考えられる。とくに、Ｖは、水素の拡散の活性化エネルギーが小さく、水素透過膜の材料として好適である。また、これらの金属及び合金は、Ｐｄ及びＰｄ合金に比べれば十分に安価であるため、製造コストの観点からも好適である。 Compared to Pd having a face-centered cubic (fcc) lattice structure, V, Nb, and Ta having a body-centered cubic (bcc) lattice structure have a smaller activation energy for hydrogen diffusion, so that the hydrogen diffusion coefficient at low temperature is higher. It has the characteristic of being large. Therefore, it is considered that a high hydrogen permeation rate can be obtained even at a relatively low temperature by using a hydrogen permeation membrane formed of these metals or alloys. In particular, V has a small activation energy for hydrogen diffusion and is suitable as a material for a hydrogen permeable membrane. Further, these metals and alloys are sufficiently cheaper than Pd and Pd alloys, and are therefore suitable from the viewpoint of manufacturing cost.
ＶやＮｂなどの５族元素は、多量の水素が固溶することで機械的性質が著しく劣化する水素脆化を起こすことが知られている。具体的には、水素濃度が約０．２（Ｈ／Ｍ）を超えると、延性−脆性遷移が起こる。したがって、水素透過膜の水素脆性破壊を回避するためには、固溶水素濃度を０．２（Ｈ／Ｍ）以下に制御する必要がある。本発明者らの知見によれば、５族元素よりも水素との親和性が小さい元素、例えば、Ｆｅ、Ｎｉ、コバルト（Ｃｏ）、クロム（Ｃｒ）、モリブデン（Ｍｏ）、タングステン（Ｗ）などや、５族元素に対する固溶限が大きいマンガン（Ｍｎ）、ルテニウム（Ｒｕ）、パラジウム（Ｐｄ）、金（Ａｕ）、レニウム（Ｒｅ）、アルミニウム（Ａｌ）、錫（Ｓｎ）、ガリウム（Ｇａ）などを５族元素に添加することにより、固溶水素濃度を抑制することができる。したがって、５族元素に上記の元素を添加した合金により水素透過膜５０を形成することにより、水素分離装置１０の使用中に水素透過膜５０が水素脆化して破断してしまうことを避けることができる。 Group 5 elements such as V and Nb are known to cause hydrogen embrittlement in which a large amount of hydrogen is dissolved in a solid solution to significantly deteriorate the mechanical properties. Specifically, when the hydrogen concentration exceeds about 0.2 (H / M), a ductile-brittle transition occurs. Therefore, in order to avoid hydrogen brittle fracture of the hydrogen permeation membrane, it is necessary to control the solid solution hydrogen concentration to 0.2 (H / M) or less. According to the findings of the present inventors, elements having a smaller affinity for hydrogen than Group 5 elements, such as Fe, Ni, cobalt (Co), chromium (Cr), molybdenum (Mo), tungsten (W), etc. Manganese (Mn), ruthenium (Ru), palladium (Pd), gold (Au), renium (Re), aluminum (Al), tin (Sn), gallium (Ga), which have a large solid solubility limit for Group 5 elements. By adding such as to Group 5 elements, the concentration of dissolved hydrogen can be suppressed. Therefore, by forming the hydrogen permeable membrane 50 with an alloy obtained by adding the above elements to the Group 5 elements, it is possible to prevent the hydrogen permeable membrane 50 from being hydrogen-brittled and broken during the use of the hydrogen separator 10. it can.
他方で、金属中に異種元素を固溶させると、固溶強化によって強度が増す上、水素透過膜５０を形成するために金属を圧延すると、加工硬化によっても強度が増すので、５族元素に添加する異種元素の量を多くし過ぎると、合金を圧延して水素透過膜５０を形成するのが難しくなる。したがって、原料気体の種類及び水素の含有量、原料気体の圧力及び温度、必要な水素の純度、単位時間当たりの水素の回収量、水素分離装置１０の耐用期間、水素分離装置１０の製造コストなどの条件に応じて、水素分離装置１０を使用する際の温度、一次側の圧力、二次側の圧力などの運転条件が決定されると、決定された運転条件に適した合金の組成を決定し、決定した組成の合金により水素透過膜５０を形成してもよい。水素透過膜５０を形成する合金の組成は、合金の水素溶解特性を表す圧力−組成−等温線（Pressure-composition-isotherm、ＰＣＴ曲線）に基づいて決定してもよい。例えば、水素透過膜５０は、原子百分率で０〜１５％のＦｅを含むＶの合金により形成されてもよい。Ｆｅの含有量を上記の範囲とすることにより、合金の強度を圧延加工が可能な程度にし、加工性を向上させることができる。温間圧延（熱間圧延）により水素透過膜５０を形成する場合には、Ｆｅの含有量を原子百分率で０〜１５％とするのが好適であり、冷間圧延により水素透過膜５０を形成する場合には、Ｆｅの含有量を原子百分率で０〜１２％とするのが好適である。圧延加工をより容易にする観点から、Ｆｅの含有量を原子百分率で０〜１０％とするのが更に好適である。 On the other hand, when a dissimilar element is dissolved in a metal, the strength is increased by strengthening the solid solution, and when the metal is rolled to form a hydrogen permeable film 50, the strength is also increased by work hardening. If the amount of dissimilar elements added is too large, it becomes difficult to roll the alloy to form the hydrogen permeable film 50. Therefore, the type and hydrogen content of the raw material gas, the pressure and temperature of the raw material gas, the required purity of hydrogen, the amount of hydrogen recovered per unit time, the useful life of the hydrogen separation device 10, the manufacturing cost of the hydrogen separation device 10, etc. When the operating conditions such as the temperature, the pressure on the primary side, and the pressure on the secondary side when using the hydrogen separator 10 are determined according to the conditions of, the composition of the alloy suitable for the determined operating conditions is determined. Then, the hydrogen permeable film 50 may be formed from the alloy having the determined composition. The composition of the alloy forming the hydrogen permeable film 50 may be determined based on the pressure-composition-isotherm (PCT curve) representing the hydrogen dissolution property of the alloy. For example, the hydrogen permeable membrane 50 may be formed of an alloy of V containing Fe in an atomic percentage of 0 to 15%. By setting the Fe content in the above range, the strength of the alloy can be adjusted to the extent that rolling can be performed, and the workability can be improved. When the hydrogen permeable film 50 is formed by warm rolling (hot rolling), it is preferable that the Fe content is 0 to 15% in terms of atomic percentage, and the hydrogen permeable film 50 is formed by cold rolling. In this case, it is preferable that the Fe content is 0 to 12% in terms of atomic percentage. From the viewpoint of facilitating the rolling process, it is more preferable that the Fe content is 0 to 10% in terms of atomic percentage.
なお、水素透過膜５０の両表面には、一次側の表面における水素分子から水素原子への解離反応、及び二次側の表面における水素原子から水素分子への再結合反応を促進するための触媒層として、Ｐｄ又はＰｄ系合金が被覆される。これにより、水素透過速度を向上させることができる。Ｐｄ又はＰｄ系合金の被覆に代えて、水素透過膜５０の両表面に酸化処理を施してもよい。 On both surfaces of the hydrogen permeation film 50, a catalyst for promoting a dissociation reaction from a hydrogen atom to a hydrogen atom on the surface on the primary side and a recombination reaction from a hydrogen atom to a hydrogen molecule on the surface on the secondary side. As a layer, Pd or a Pd-based alloy is coated. Thereby, the hydrogen permeation rate can be improved. Instead of coating with Pd or a Pd-based alloy, both surfaces of the hydrogen permeable membrane 50 may be subjected to an oxidation treatment.
図１に示した水素分離装置１０においては、原料気体供給流路２６及び水素回収流路３２が水素透過膜５０に対して垂直に設けられるが、別の例では、原料気体供給流路２６又は水素回収流路３２が水素透過膜５０に平行に設けられてもよいし、任意の方向に設けられてもよい。また、図１に示した水素分離装置１０においては、原料気体排出流路２８も水素透過膜５０に対して垂直に設けられるが、別の例では、水素透過膜５０を透過しなかった原料気体は、水素透過膜５０の外周の近傍に設けられた排出口から排出されてもよい。 In the hydrogen separation device 10 shown in FIG. 1, the raw material gas supply flow path 26 and the hydrogen recovery flow path 32 are provided perpendicular to the hydrogen permeation film 50, but in another example, the raw material gas supply flow path 26 or The hydrogen recovery flow path 32 may be provided parallel to the hydrogen permeation film 50, or may be provided in any direction. Further, in the hydrogen separation device 10 shown in FIG. 1, the raw material gas discharge flow path 28 is also provided perpendicular to the hydrogen permeable membrane 50, but in another example, the raw material gas that did not permeate the hydrogen permeable membrane 50. May be discharged from a discharge port provided near the outer periphery of the hydrogen permeable membrane 50.
［水素透過膜の耐久性を向上させるための技術］
つづいて、Ｐｄ系合金が触媒層として被覆された非Ｐｄ系金属又は非Ｐｄ系合金の水素透過膜（以下、「複合膜」ともいう）を使用する水素透過装置において、複合膜の水素透過性能及び耐久性を向上させる技術について説明する。
[Technology for improving the durability of hydrogen permeable membrane]
Subsequently, in a hydrogen permeation device using a hydrogen permeation membrane (hereinafter, also referred to as “composite membrane”) of a non-Pd metal or non-Pd alloy coated with a Pd alloy as a catalyst layer, the hydrogen permeation performance of the composite membrane And the technique for improving durability will be described.
［触媒層の組成の制御］
図２は、純Ｖの水素透過膜に純Ｐｄの触媒層を被覆した複合膜の５５０℃における水素透過能の時間変化を示す。一次側の圧力は４００ｋＰａとし、二次側の圧力は２００ｋＰａとした。水素の供給を開始してすぐに透過流速が減少し始め、わずか３０分でほぼゼロになった。複合膜を高温下で使用したことにより水素透過膜のＶと触媒層のＰｄが相互拡散したことが、このような水素透過能の急速な劣化の主要な要因の一つであろうと推測される。
[Control of catalyst layer composition]
FIG. 2 shows the time change of the hydrogen permeability at 550 ° C. of a composite membrane in which a pure V hydrogen permeable membrane is coated with a pure Pd catalyst layer. The pressure on the primary side was 400 kPa, and the pressure on the secondary side was 200 kPa. Immediately after starting the supply of hydrogen, the permeation flow rate began to decrease and became almost zero in just 30 minutes. It is speculated that the mutual diffusion of V of the hydrogen permeable membrane and Pd of the catalyst layer due to the use of the composite membrane at high temperature may be one of the major causes of such rapid deterioration of hydrogen permeability. ..
図３は、ＶとＦｅの合金の水素透過膜にＰｄとＡｇの合金の触媒層を被覆した複合膜の３００℃における水素透過能の時間変化を示す。一次側の圧力は２００ｋＰａとし、二次側の圧力は１０ｋＰａとした。水素透過膜は、原子百分率でＦｅを１０％含むＶにより形成されたものであり、触媒層は、原子百分率でＡｇを２７％含むＰｄで形成されたものである。透過流速は、４０日以上経過してもほとんど減少しておらず、図２に示した場合に比べて非常に高い安定性を有することが分かった。 FIG. 3 shows the time change of the hydrogen permeability at 300 ° C. of the composite membrane in which the hydrogen permeable membrane of the alloy of V and Fe is coated with the catalyst layer of the alloy of Pd and Ag. The pressure on the primary side was 200 kPa, and the pressure on the secondary side was 10 kPa. The hydrogen permeable membrane is formed of V containing 10% of Fe in the atomic percentage, and the catalyst layer is formed of Pd containing 27% of Ag in the atomic percentage. It was found that the permeation flow velocity hardly decreased even after 40 days or more, and had a very high stability as compared with the case shown in FIG.
以上の結果より、複合膜の劣化速度を抑え、耐久性を向上させるためには、使用温度を低くすることも有効な手段の一つであるが、触媒層として純ＰｄではなくＰｄ系合金を使用することも、耐久性の向上に寄与することが示唆される。 From the above results, in order to suppress the deterioration rate of the composite film and improve the durability, lowering the operating temperature is one of the effective means, but a Pd-based alloy is used as the catalyst layer instead of pure Pd. It is suggested that the use also contributes to the improvement of durability.
そこで、本発明者らは、触媒層におけるＰｄとＡｇの組成が異なる複数の複合膜の試料を作製して水素透過試験を実施し、触媒層を形成するＰｄ系合金におけるＰｄとＡｇの最適な組成を検討した。 Therefore, the present inventors prepared a sample of a plurality of composite membranes having different compositions of Pd and Ag in the catalyst layer, conducted a hydrogen permeation test, and optimally selected Pd and Ag in the Pd-based alloy forming the catalyst layer. The composition was examined.
Ｆｅを原子百分率で１０％含むＶの合金（Ｖ−１０％Ｆｅ）により形成された水素透過膜（厚さ：１００μｍ）を洗浄し、１０００℃で２４時間熱処理した後、ＲＦスパッタリングによりＰｄ合金（Ｐｄ−ｘ％Ａｇ）を両面に約２００ｎｍ被覆して複合膜の試料を作製した。複合膜を水素分離装置１０の水素透過膜５０として設置し、温度３５０℃、一次側圧力４００ｋＰａ、二次側圧力１０３ｋＰａの条件で透過流速が安定するまで運転した後、温度４５０℃、５００℃、又は５５０℃まで急速に昇温し、一次側圧力４００ｋＰａ、二次側圧力１０３ｋＰａで水素透過試験を実施し、水素透過流速の経時変化を記録した。 A hydrogen permeable film (thickness: 100 μm) formed of a V alloy (V-10% Fe) containing 10% of Fe in atomic percentage is washed, heat-treated at 1000 ° C. for 24 hours, and then Pd alloy (Pd alloy) by RF sputtering. Pd-x% Ag) was coated on both sides at about 200 nm to prepare a composite film sample. The composite film was installed as the hydrogen permeable film 50 of the hydrogen separator 10 and operated under the conditions of a temperature of 350 ° C., a primary side pressure of 400 kPa, and a secondary side pressure of 103 kPa until the permeation flow velocity became stable, and then the temperatures were 450 ° C. and 500 ° C. Alternatively, the temperature was rapidly raised to 550 ° C., a hydrogen permeation test was carried out at a primary side pressure of 400 kPa and a secondary side pressure of 103 kPa, and changes over time in the hydrogen permeation flow velocity were recorded.
図４は、ＶとＦｅの合金の水素透過膜にＰｄとＡｇの合金の触媒層を被覆した複合膜の５５０℃における水素透過能の時間変化を示す。上記の手順により作製したＶ−１０％Ｆｅの水素透過膜にＰｄ−２７％Ａｇを被覆した複合膜を５５０℃で使用した場合、図３に示した３００℃で使用した場合よりも速く透過流速が減少するが、図２に示した純Ｐｄを純Ｖ膜に被覆した場合と比較して耐久性が高い。透過流速が開始直後の透過流速から２０％減少した時点までの時間を２０％劣化時間ｔ０．２と定義すると、Ｖ−１０％Ｆｅの水素透過膜にＰｄ−２７％Ａｇを被覆した複合膜を５５０℃で使用した場合の２０％劣化時間ｔ０．２は、図４に示すように、３．３時間である。 FIG. 4 shows the time change of the hydrogen permeability at 550 ° C. of the composite membrane in which the hydrogen permeable membrane of the alloy of V and Fe is coated with the catalyst layer of the alloy of Pd and Ag. When a composite membrane in which a hydrogen permeable membrane of V-10% Fe prepared by the above procedure is coated with Pd-27% Ag is used at 550 ° C., the permeation flow velocity is faster than when it is used at 300 ° C. shown in FIG. However, the durability is higher than that in the case where the pure Pd shown in FIG. 2 is coated on the pure V film. If the time from the permeation flow velocity immediately after the start to the time when the permeation flow velocity decreases by 20% is defined as the 20% deterioration time t 0.2 , a composite membrane in which a hydrogen permeation membrane of V-10% Fe is coated with Pd-27% Ag. The 20% deterioration time t 0.2 when used at 550 ° C. is 3.3 hours as shown in FIG.
図５は、触媒層の組成と劣化時間との関係を示す。４５０℃における水素透過試験では、触媒層におけるＡｇの濃度が約２０〜３０％のときにｔ０．２が最大となった。５００℃における水素透過試験では、触媒層におけるＡｇの濃度が約１０〜３０％のときにｔ０．２が最大となった。５５０℃における水素透過試験では、触媒層におけるＡｇの濃度が約１０〜２５％のときにｔ０．２が最大となった。 FIG. 5 shows the relationship between the composition of the catalyst layer and the deterioration time. In the hydrogen permeation test at 450 ° C., t 0.2 was the maximum when the concentration of Ag in the catalyst layer was about 20 to 30%. In the hydrogen permeation test at 500 ° C., t 0.2 was the maximum when the concentration of Ag in the catalyst layer was about 10 to 30%. In the hydrogen permeation test at 550 ° C., t 0.2 was the maximum when the concentration of Ag in the catalyst layer was about 10 to 25%.
以上の結果より、複合膜の触媒層を形成するＰｄ系合金におけるＡｇの最適な濃度は、５〜４０％、より好ましくは５〜３０％、更に好ましくは１０〜３０％である。より具体的には、４５０℃において複合膜を使用する場合の触媒層のＡｇの最適な濃度は、劣化時間ｔ０．２が４０時間以上となる５〜４０％、より好ましくは劣化時間ｔ０．２が７０時間以上となる７〜４０％、更に好ましくは劣化時間ｔ０．２が１００時間以上となる１０〜３５％である。５００℃において複合膜を使用する場合の触媒層のＡｇの最適な濃度は、劣化時間ｔ０．２が２時間以上となる２〜４０％、より好ましくは劣化時間ｔ０．２が５時間以上となる５〜４０％、更に好ましくは劣化時間ｔ０．２が１０時間以上となる１０〜４０％、更に好ましくは劣化時間ｔ０．２が２０時間以上となる１５〜３０％である。５５０℃において複合膜を使用する場合の触媒層のＡｇの最適な濃度は、劣化時間ｔ０．２が０．８時間以上となる５〜４０％、より好ましくは劣化時間ｔ０．２が２時間以上となる１０〜３５％、更に好ましくは劣化時間ｔ０．２が３時間以上となる１５〜３０％である。 From the above results, the optimum concentration of Ag in the Pd-based alloy forming the catalyst layer of the composite film is 5 to 40%, more preferably 5 to 30%, still more preferably 10 to 30%. More specifically, the optimum concentration of Ag in the catalyst layer when the composite membrane is used at 450 ° C. is 5 to 40% when the deterioration time t 0.2 is 40 hours or more, more preferably the deterioration time t 0. .2 is 7 to 40% when it is 70 hours or more, and more preferably 10 to 35% when the deterioration time t 0.2 is 100 hours or more. When the composite membrane is used at 500 ° C., the optimum concentration of Ag in the catalyst layer is 2 to 40% in which the deterioration time t 0.2 is 2 hours or more, and more preferably the deterioration time t 0.2 is 5 hours or more. It is 5 to 40%, more preferably 10 to 40% in which the deterioration time t 0.2 is 10 hours or more, and further preferably 15 to 30% in which the deterioration time t 0.2 is 20 hours or more. When the composite membrane is used at 550 ° C., the optimum concentration of Ag in the catalyst layer is 5 to 40% when the deterioration time t 0.2 is 0.8 hours or more, and more preferably the deterioration time t 0.2 is 2. The time is 10 to 35%, more preferably the deterioration time t 0.2 is 15 to 30%, which is 3 hours or more.
図６は、水素透過試験温度に対する劣化時間の変化を示す。横軸は水素透過試験温度の逆数であり、縦軸は劣化時間の逆数を劣化速度としてプロットしている。温度の逆数に対して、２０％劣化速度ｒｄｅｇ＿０．２（＝１／ｔ０．２）をプロットすると、ほぼ直線となる。したがって、近似式により複合膜の寿命を推測することができる。原子百分率で５〜４０％のＡｇを含むＰｄ合金の触媒層を被覆した複合膜は、純Ｐｄの触媒層を被覆した複合膜よりも劣化速度が遅く、耐久性が高いことが分かる。１０〜２０％のＡｇを含むＰｄ合金の触媒層を被覆した複合膜は、とくに耐久性が高い。 FIG. 6 shows the change in the deterioration time with respect to the hydrogen permeation test temperature. The horizontal axis is the reciprocal of the hydrogen permeation test temperature, and the vertical axis is the reciprocal of the deterioration time plotted as the deterioration rate. When the 20% deterioration rate r deg_0.2 (= 1 / t 0.2 ) is plotted against the reciprocal of the temperature, it becomes almost a straight line. Therefore, the life of the composite film can be estimated from the approximate expression. It can be seen that the composite film coated with the catalyst layer of the Pd alloy containing Ag at an atomic percentage of 5 to 40% has a slower deterioration rate and higher durability than the composite film coated with the catalyst layer of pure Pd. A composite membrane coated with a catalyst layer of a Pd alloy containing 10 to 20% Ag has particularly high durability.
本開示に係る水素透過装置において、Ａｇ以外の金属元素を含むＰｄ系合金を触媒層としてもよい。ＡｇとＡｇ以外の金属元素の双方を含むＰｄ系合金を触媒層としてもよい。Ａｇ以外の金属元素は、例えば、Ｗであってもよい。 In the hydrogen permeation apparatus according to the present disclosure, a Pd-based alloy containing a metal element other than Ag may be used as the catalyst layer. A Pd-based alloy containing both Ag and a metal element other than Ag may be used as the catalyst layer. The metal element other than Ag may be, for example, W.
図７は、触媒層の組成と透過流速比の時間変化との関係を示す。Ｖ−１０％Ｆｅの水素透過膜にＡｇを２８％とＷを０．８％含むＰｄ系合金を触媒層として被覆した複合膜は、Ａｇを２７％含むＰｄ系合金を触媒層として被覆した複合膜よりも更に高い耐久性を有することが示された。 FIG. 7 shows the relationship between the composition of the catalyst layer and the time change of the permeation flow velocity ratio. The composite membrane in which a V-10% Fe hydrogen permeable membrane is coated with a Pd-based alloy containing 28% Ag and 0.8% W as a catalyst layer is a composite membrane coated with a Pd-based alloy containing 27% Ag as a catalyst layer. It has been shown to have even higher durability than membranes.
したがって、本開示に係る水素透過装置は、純金属又は合金により形成された水素透過膜と、前記水素透過膜の表面にパラジウムと銀の合金により形成された触媒層と、を備え、前記触媒層におけるパラジウムと銀の組成比は、一次側圧力が４００ｋＰａ、二次側圧力が１０３ｋＰａ、温度が４５０℃、５００℃、又は５５０℃の条件下で前記水素透過膜の水素透過試験を実施した場合に透過流速が開始直後の透過流速から２０％減少する時点までの時間である２０％劣化時間ｔ０．２が［００３０］〜［００３１］に上述した値の範囲となるような組成比であることを特徴とする。例えば、ＰｄとＡｇの合金を使用する場合、Ａｇの含有量は上述した値の範囲であってもよい。この態様によると、水素透過装置の耐久性を向上させることができる。 Therefore, the hydrogen permeation apparatus according to the present disclosure includes a hydrogen permeation membrane formed of a pure metal or an alloy, and a catalyst layer formed of an alloy of palladium and silver on the surface of the hydrogen permeation membrane. The composition ratio of palladium and silver in the above is when the hydrogen permeation test of the hydrogen permeation membrane is carried out under the conditions of a primary side pressure of 400 kPa, a secondary side pressure of 103 kPa, and a temperature of 450 ° C., 500 ° C., or 550 ° C. The composition ratio is such that the 20% deterioration time t 0.2, which is the time from the permeation flow velocity immediately after the start to the time when the permeation flow velocity decreases by 20%, is in the range of the above-mentioned values in [0030] to [0031]. It is characterized by. For example, when an alloy of Pd and Ag is used, the Ag content may be in the range of the above-mentioned values. According to this aspect, the durability of the hydrogen permeation device can be improved.
［水素透過膜の結晶方位の制御］
本発明者らは、上述した水素透過試験の実施後に、複合膜の表面の走査型電子顕微鏡（ＳＥＭ）像の解析及びエネルギー分散型Ｘ線分析（ＥＤＸ）を実施した結果、結晶方位によって劣化の挙動が異なるという知見を得た。そこで、Ｖ合金の膜の表面にＰｄ層を被覆した複合膜の熱処理による構造変化とＶ合金の結晶方位との関係を調査した。
[Control of crystal orientation of hydrogen permeable membrane]
After the above-mentioned hydrogen permeation test, the present inventors performed a scanning electron microscope (SEM) image analysis and an energy dispersive X-ray analysis (EDX) on the surface of the composite film, and as a result, the deterioration was caused by the crystal orientation. We obtained the finding that the behavior is different. Therefore, the relationship between the structural change due to heat treatment of the composite film in which the surface of the V alloy film was coated with the Pd layer and the crystal orientation of the V alloy was investigated.
まず、高純度Ｖを冷間鍛造し、切削加工により２ｍｍ×１０ｍｍ×１０ｍｍの試料片を作製した。この試料片を、５×１０−３Ｐａ、１０００℃で３０分間熱処理した後、１μｍのダイヤモンドパッドで研磨し、バフ仕上げ、アルゴンイオンミリングを実施した。この熱処理前の試料の表面を光学顕微鏡で観察するとともに、電子線後方散乱回折（Electron Back Scattered Diffraction Pattern：ＥＢＳＤ）法により結晶方位を解析した。つづいて、試料片の表面をＰｄ−Ａｇ合金で被覆し、５×１０−３Ｐａ、５００℃で２４時間熱処理した。この熱処理後の試料の表面を光学顕微鏡で観察するとともに、ＥＢＳＤ法により結晶方位を解析した。 First, high-purity V was cold forged, and a sample piece of 2 mm × 10 mm × 10 mm was prepared by cutting. This sample piece was heat-treated at 5 × 10 -3 Pa at 1000 ° C. for 30 minutes, polished with a 1 μm diamond pad, buffed, and subjected to argon ion milling. The surface of the sample before this heat treatment was observed with an optical microscope, and the crystal orientation was analyzed by the Electron Back Scattered Diffraction Pattern (EBSD) method. Subsequently, the surface of the sample piece was coated with a Pd-Ag alloy and heat-treated at 5 × 10 -3 Pa at 500 ° C. for 24 hours. The surface of the sample after this heat treatment was observed with an optical microscope, and the crystal orientation was analyzed by the EBSD method.
図８は、熱処理後の複合膜の表面のＳＥＭ像である。複合膜の表面には、結晶方位の異なる複数の結晶粒が形成されている。図８に示した（１）〜（７）の位置において、表面と断面の構造を分析した。（１）〜（４）は、結晶方位が＜１１１＞方位である結晶粒に対応し、（５）及び（６）は、結晶方位が＜１０１＞方位である結晶粒に対応し、（７）は、結晶方位が＜１０１＞方位である結晶粒と別の方位である結晶粒との粒界部分に対応する。なお、Ｖは体心立方格子構造を有しており、［１１０］、［１０１］、［０１１］などの方位は結晶学的に等価であるから、代表して＜１０１＞と表記する。 FIG. 8 is an SEM image of the surface of the composite film after the heat treatment. A plurality of crystal grains having different crystal orientations are formed on the surface of the composite film. The surface and cross-sectional structures were analyzed at the positions (1) to (7) shown in FIG. (1) to (4) correspond to crystal grains having a crystal orientation of <111> orientation, and (5) and (6) correspond to crystal grains having a crystal orientation of <101> orientation, and (7). ) Corresponds to the grain boundary portion between the crystal grains whose crystal orientation is the <101> orientation and the crystal grains whose orientation is another orientation. Since V has a body-centered cubic lattice structure and the orientations of [110], [101], [011] and the like are crystallographically equivalent, it is represented as <101>.
図９は、図８に示した複合膜の（１）〜（７）の位置のＳＥＭ像である。結晶方位が＜１０１＞方位である（５）の表面は、その他の表面に比べて平坦であり、熱処理による劣化が少ないことが示された。なお、（６）も結晶方位が＜１０１＞方位である結晶粒に対応しているが、欠陥に起因すると思われる凹凸が生じている。 FIG. 9 is an SEM image of the positions (1) to (7) of the composite film shown in FIG. It was shown that the surface of (5) having a crystal orientation of <101> orientation was flatter than the other surfaces and was less deteriorated by heat treatment. It should be noted that (6) also corresponds to the crystal grains whose crystal orientation is <101> orientation, but irregularities that are considered to be caused by defects are generated.
図１０は、図８に示した複合膜の（１）〜（７）の位置の断面のＳＥＭ像である。結晶方位が＜１０１＞方位である（５）の断面は、Ｐｄ層とＶ合金膜との間の相互拡散がほとんどなく、触媒層と水素透過膜の構造が良好に維持されている。 FIG. 10 is an SEM image of a cross section of the composite film shown in FIG. 8 at positions (1) to (7). In the cross section of (5) in which the crystal orientation is <101> orientation, there is almost no mutual diffusion between the Pd layer and the V alloy film, and the structure of the catalyst layer and the hydrogen permeation membrane is well maintained.
図１１は、熱処理後の複合膜のオージェ電子分光法（Auger Electron Spectroscopy：ＡＥＳ）による分析結果を結晶方位ごとに示す。同じ酸素分圧下であっても、結晶方位によってＶの挙動が異なっている。ＰｄとＶの相互拡散は、＜１０１＞方位、＜００１＞方位、＜１１１＞方位の順に大きくなっている。 FIG. 11 shows the analysis results of the composite film after the heat treatment by Auger Electron Spectroscopy (AES) for each crystal orientation. Even under the same oxygen partial pressure, the behavior of V differs depending on the crystal orientation. The mutual diffusion of Pd and V increases in the order of <101> azimuth, <001> azimuth, and <111> azimuth.
以上の実験結果から、Ｖ合金の表面をＰｄ−Ａｇ合金で被覆した複合膜を熱処理したときのＰｄとＶの相互拡散は結晶方位によって異なり、＜１０１＞方位、＜００１＞方位、＜１１１＞方位の順に大きくなることが示された。したがって、結晶方位を＜１０１＞方位に配向させたＶ合金を使用することにより、Ｖ合金とＰｄ−Ａｇ合金の複合膜の耐久性を向上させることができると考えられる。 From the above experimental results, the mutual diffusion of Pd and V when the composite film in which the surface of the V alloy is coated with the Pd-Ag alloy is heat-treated differs depending on the crystal orientation, and is different depending on the crystal orientation, <101> orientation, <001> orientation, and <111>. It was shown to increase in the order of orientation. Therefore, it is considered that the durability of the composite film of the V alloy and the Pd-Ag alloy can be improved by using the V alloy in which the crystal orientation is oriented in the <101> orientation.
上記の知見を確認するために、（１１０）、（１１１）、及び（１００）の面方位を有する純Ｖ単結晶の表面にＰｄ−２５Ａｇを被覆した試料を用いて４００℃で連続水素透過試験を実施し、複合膜の耐久性を評価した。１次側水素圧力は２０ｋＰａとし、２次側圧力は真空とした。試料の厚さは、（１１０）方位は０．３１９ｍｍ、（１１１）方位は０．４４９ｍｍ、（１００）方位は０．５６８ｍｍであった。 In order to confirm the above findings, a continuous hydrogen permeation test at 400 ° C. was performed using a sample in which the surface of a pure V single crystal having the plane orientations of (110), (111), and (100) was coated with Pd-25Ag. Was carried out, and the durability of the composite film was evaluated. The hydrogen pressure on the primary side was 20 kPa, and the pressure on the secondary side was vacuum. The thickness of the sample was 0.319 mm in the (110) orientation, 0.449 mm in the (111) orientation, and 0.568 mm in the (100) orientation.
図１２は、純Ｖ単結晶試料を用いた連続水素透過試験の結果を示す。試験開始から１６８時間後の水素透過度は、結晶方位によって顕著に異なっている。（１１０）方位の試料では、水素透過度が１６８時間経過後もほとんど低下しておらず、高い耐久性を有することが示された。水素透過度の劣化速度は、（１１０）方位＜（１１１）方位＜（１００）方位の順に速くなる。 FIG. 12 shows the results of a continuous hydrogen permeation test using a pure V single crystal sample. The hydrogen permeability after 168 hours from the start of the test is significantly different depending on the crystal orientation. In the sample in the (110) orientation, the hydrogen permeability was hardly reduced even after the lapse of 168 hours, indicating that the sample had high durability. The deterioration rate of hydrogen permeability increases in the order of (110) orientation <(111) orientation <(100) orientation.
図１３は、水素透過試験前後の純Ｖ単結晶試料の表面のＳＥＭ像である。図１３（ａ）は、純Ｖ単結晶の表面にＰｄ−２５Ａｇをスパッタリングした直後のＳＥＭ像であり、図１３（ｂ）は、連続水素透過試験後のＳＥＭ像である。（１１０）面は、連続水素透過試験後も平坦であり、良好な状態が維持されている。（１００）面及び（１１１）面は、連続水素透過試験後には表面に凹凸が生じており、ＰｄとＶが相互拡散したことが示唆される。 FIG. 13 is an SEM image of the surface of the pure V single crystal sample before and after the hydrogen permeation test. FIG. 13 (a) is an SEM image immediately after sputtering Pd-25Ag on the surface of a pure V single crystal, and FIG. 13 (b) is an SEM image after a continuous hydrogen permeation test. The surface (110) is flat even after the continuous hydrogen permeation test, and is maintained in a good state. The surfaces of the (100) and (111) planes have irregularities after the continuous hydrogen permeation test, suggesting that Pd and V are mutually diffused.
したがって、本開示に係る水素透過装置は、純金属又は合金により形成された水素透過膜と、前記水素透過膜の表面に設けられた触媒層と、を備え、前記触媒層との境界面における前記水素透過膜の金属又は合金の所定比率以上が特定の結晶方位に配向したことを特徴とする。この態様によると、水素透過装置の耐久性などの特性を向上させることができる。 Therefore, the hydrogen permeation device according to the present disclosure includes a hydrogen permeation membrane formed of a pure metal or alloy and a catalyst layer provided on the surface of the hydrogen permeation membrane, and the hydrogen permeation device at the interface with the catalyst layer. It is characterized in that more than a predetermined ratio of the metal or alloy of the hydrogen permeable membrane is oriented in a specific crystal orientation. According to this aspect, characteristics such as durability of the hydrogen permeation device can be improved.
水素透過膜は、体心立方格子構造を有する金属元素の純金属又は合金により形成されてもよい。水素透過膜は、５族元素の純金属又は５族元素を主たる金属とする合金により形成されてもよい。水素透過膜は、Ｖの純金属又はＶとＦｅの合金により形成されてもよい。 The hydrogen permeable membrane may be formed of a pure metal or alloy of a metal element having a body-centered cubic lattice structure. The hydrogen permeable membrane may be formed of a pure metal of a Group 5 element or an alloy containing a Group 5 element as a main metal. The hydrogen permeable membrane may be formed of a pure metal of V or an alloy of V and Fe.
触媒層は、純Ｐｄ、又は、Ｐｄを主たる金属とする合金により形成されてもよい。触媒層は、ＰｄとＡｇ及びＷのうち一方若しくは双方との合金により形成されてもよい。 The catalyst layer may be formed of pure Pd or an alloy containing Pd as a main metal. The catalyst layer may be formed of an alloy of Pd and one or both of Ag and W.
Ｐｄ系合金におけるＰｄとＰｄ以外の金属元素との組成比は、一次側圧力が４００ｋＰａ、二次側圧力が１０３ｋＰａ、温度が４５０℃、５００℃、又は５５０℃の条件下で水素透過膜の水素透過試験を実施した場合に透過流速が開始直後の透過流速から２０％減少する時点までの時間である２０％劣化時間ｔ０．２が［００３０］〜［００３１］に上述した値の範囲となるような組成比であってもよい。例えば、ＰｄとＡｇの合金を使用する場合、Ａｇの含有量は［００３０］〜［００３２］に上述した値の範囲であってもよい。 The composition ratio of Pd and metal elements other than Pd in the Pd alloy is as follows: hydrogen in the hydrogen permeation film under the conditions of a primary pressure of 400 kPa, a secondary pressure of 103 kPa, and a temperature of 450 ° C, 500 ° C, or 550 ° C. When the permeation test is carried out, the 20% deterioration time t 0.2, which is the time from the permeation flow velocity immediately after the start to the time when the permeation flow velocity decreases by 20%, is in the range of the above-mentioned values in [0030] to [0031]. The composition ratio may be such that. For example, when an alloy of Pd and Ag is used, the content of Ag may be in the range of the above-mentioned values in [0030] to [0032].
特定の結晶方位は、＜１０１＞方位であってもよい。この態様によると、水素透過膜を構成する金属原子と触媒層を構成する金属原子との相互拡散を抑えることができるので、水素透過装置の耐久性を向上させることができる。 The specific crystal orientation may be the <101> orientation. According to this aspect, the mutual diffusion between the metal atoms constituting the hydrogen permeation membrane and the metal atoms constituting the catalyst layer can be suppressed, so that the durability of the hydrogen permeation device can be improved.
水素透過膜の表面において、特定の結晶方位に配向した領域の比率は、例えば、１０％以上、２０％以上、３０％以上、４０％以上、５０％以上、６０％以上、７０％以上、８０％以上、９０％以上であってもよい。特定の結晶方位に配向した領域が、他の結晶方位に配向した領域よりも大きくてもよい。結晶方位の比率は、上述したＥＢＳＤ法による解析により算出することができる。 On the surface of the hydrogen permeable membrane, the proportions of regions oriented in a specific crystal orientation are, for example, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80. It may be% or more and 90% or more. The region oriented in a particular crystal orientation may be larger than the region oriented in another crystal orientation. The ratio of crystal orientations can be calculated by the analysis by the EBSD method described above.
上述したように、水素透過装置の耐久性を向上させる観点からは、水素透過膜を形成する純金属又は合金の結晶方位を＜１０１＞方位に配向させることが好ましいが、別の観点からは、別の方位に配向させることが好ましい場合もある。例えば、流体に含まれる水素を除去するために水素透過装置を使用する場合、流体に含まれる水素が選択的に水素透過膜を透過して除去された後、いったん水素透過膜を透過した水素が一次側圧力と二次側圧力との圧力差が逆転するなどの要因により流体側に戻ってしまうのを防ぐことが好ましい。このような観点からは、水素透過膜の使用後に水素透過能が速やかに失活するように、水素透過膜を形成する純金属又は合金の結晶方位を＜００１＞方位又は＜１１１＞方位に配向させてもよい。 As described above, from the viewpoint of improving the durability of the hydrogen permeation device, it is preferable to orient the crystal orientation of the pure metal or alloy forming the hydrogen permeation membrane in the <101> orientation, but from another viewpoint, it is preferable. It may be preferable to orient it in a different orientation. For example, when a hydrogen permeation device is used to remove hydrogen contained in a fluid, hydrogen contained in the fluid is selectively permeated through the hydrogen permeation film to be removed, and then hydrogen once permeated through the hydrogen permeation film is removed. It is preferable to prevent the pressure difference between the primary side pressure and the secondary side pressure from returning to the fluid side due to factors such as reversal. From this point of view, the crystal orientation of the pure metal or alloy forming the hydrogen permeable membrane is oriented in the <001> orientation or the <111> orientation so that the hydrogen permeability is rapidly deactivated after the use of the hydrogen permeable membrane. You may let me.
［薄膜の結晶方位の制御方法］
特定の結晶方位に配向した純金属又は合金の薄膜を製造するための方法として、金属単結晶を形成するなど、既知の任意の技術を利用可能である。本開示では、より安価で容易な方法として、純金属又は合金により水素透過膜を形成するステップと、水素透過膜の表面の純金属又は合金のうち特定の結晶方位に配向した領域を増加させるステップと、を備える製造方法を新たに提案する。特定の結晶方位に配向した領域を増加させるステップは、水素透過膜の表面の純金属又は合金の結晶粒径を微細化するための処理を実行するステップを含んでもよい。結晶粒径を微細化するための処理は、任意の技術を利用してもよいが、例えば、以下の４つの方法がある。第１の方法は、水素透過膜の表面をショットブラスト加工する方法である。第２の方法は、アークプラズマ法により水素透過膜の表面に金属原子を蒸着させる方法である。第３の方法は、水素透過膜を高圧ねじり（High-Pressure Torsion：ＨＰＴ）加工する方法である。第４の方法は、水素透過膜を高圧スライド（High-Pressure Sliding：ＨＰＳ）加工する方法である。ショットブラスト加工、アークプラズマ法による蒸着、高圧ねじり加工、高圧スライド加工は、いずれも、既知の任意の技術を利用可能である。特定の結晶方位に配向した領域を増加させるステップは、熱処理を実行するステップを含んでもよい。
[Method of controlling crystal orientation of thin film]
Any known technique is available, such as forming a metal single crystal, as a method for producing a thin film of pure metal or alloy oriented in a particular crystal orientation. In the present disclosure, as a cheaper and easier method, a step of forming a hydrogen permeable membrane from a pure metal or alloy and a step of increasing a region of the pure metal or alloy on the surface of the hydrogen permeable membrane oriented in a specific crystal orientation. We propose a new manufacturing method that includes. The step of increasing the region oriented in a specific crystal orientation may include a step of performing a process for refining the crystal grain size of a pure metal or alloy on the surface of a hydrogen permeable membrane. Any technique may be used for the treatment for refining the crystal grain size, and for example, there are the following four methods. The first method is a method of shot blasting the surface of the hydrogen permeable membrane. The second method is a method of depositing metal atoms on the surface of a hydrogen permeable membrane by an arc plasma method. The third method is a method of processing a hydrogen permeable membrane by high-pressure torsion (HPT). The fourth method is a method of high-pressure sliding (HPS) processing of a hydrogen permeable membrane. Any known technique can be used for shot blasting, vapor deposition by the arc plasma method, high-pressure twisting, and high-pressure sliding. The step of increasing the region oriented in a particular crystal orientation may include performing a heat treatment.
図１４は、本開示に係る第１の方法により製造した薄膜のＸ線回折結果を示す。最上段は、圧延により製造した試料のＸ線回折結果を示す。圧延により（１１０）面のピークはほぼ消失しており、（２００）面や（２１１）面のピークが優勢となる。中段は、圧延した試料の表面をショットブラスト加工した試料のＸ線回折結果を示す。ショットブラスト加工により（１１０）面のピークが優勢となる。このＸ線回折結果は、結晶がランダムに配向した試料のものとほぼ同様である。すなわち、ショットブラスト加工により表面の結晶粒をランダムに配向させることができるので、圧延によりほぼ消失してしまった（１１０）面に配向した結晶粒を再び生じさせ、増加させることができる。最下段は、ショットブラスト加工した試料を、８００℃、５×１０−３Ｐａで１５分間熱処理した試料のＸ線回折結果を示す。熱処理により、それぞれのピークが急峻になっている。 FIG. 14 shows the X-ray diffraction result of the thin film produced by the first method according to the present disclosure. The top row shows the X-ray diffraction results of the sample produced by rolling. By rolling, the peak on the (110) plane has almost disappeared, and the peaks on the (200) plane and the (211) plane become dominant. The middle stage shows the X-ray diffraction results of the sample obtained by shotblasting the surface of the rolled sample. Due to shot blasting, the peak on the (110) surface becomes predominant. The result of this X-ray diffraction is almost the same as that of the sample in which the crystals are randomly oriented. That is, since the crystal grains on the surface can be randomly oriented by the shot blasting process, the crystal grains oriented on the (110) plane, which has almost disappeared by rolling, can be regenerated and increased. The bottom row shows the X-ray diffraction results of the shot-blasted sample heat-treated at 800 ° C. and 5 × 10 -3 Pa for 15 minutes. Due to the heat treatment, each peak becomes steep.
図１５は、本開示に係る第２の方法により製造した薄膜のＸ線回折結果を示す。最上段は、図１４の最上段と同じ圧延後の試料のＸ線回折結果を示す。中段は、圧延した試料の表面にアークプラズマ法によりＦｅ原子を蒸着させた試料のＸ線回折結果を示す。薄膜の表面に被覆されたＦｅは、主に（１１０）面に配向している。したがって、試料の表面にアークプラズマ法により金属原子を蒸着させることにより、特定の結晶方位に配向した領域を増加させることができる。最下段は、Ｆｅ原子を蒸着させた試料を、５００℃、５×１０−３Ｐａ以下で１時間熱処理した試料のＸ線回折結果を示す。熱処理によりＦｅの（１１０）面のピークがやや成長している。したがって、試料の表面にアークプラズマ法により金属原子を蒸着させた後、熱処理を実施することにより、特定の結晶方位に配向した領域を更に増加させることができる。 FIG. 15 shows the X-ray diffraction results of the thin film produced by the second method according to the present disclosure. The uppermost stage shows the same X-ray diffraction results of the sample after rolling as in the uppermost stage of FIG. The middle stage shows the X-ray diffraction results of the sample in which Fe atoms are vapor-deposited on the surface of the rolled sample by the arc plasma method. The Fe coated on the surface of the thin film is mainly oriented on the (110) plane. Therefore, by depositing metal atoms on the surface of the sample by the arc plasma method, it is possible to increase the region oriented in a specific crystal orientation. The bottom row shows the X-ray diffraction results of the sample in which the Fe atom-deposited sample is heat-treated at 500 ° C. and 5 × 10 -3 Pa or less for 1 hour. The peak of the (110) plane of Fe is slightly grown by the heat treatment. Therefore, by depositing metal atoms on the surface of the sample by the arc plasma method and then performing heat treatment, the region oriented in a specific crystal orientation can be further increased.
図１６は、本開示に係る第３の方法により製造した薄膜のＸ線回折結果を示す。最上段は、図１４の最上段と同じ圧延後の試料のＸ線回折結果を示す。中段は、圧延した試料の表面を高圧ねじり加工した試料のＸ線回折結果を示す。高圧ねじり加工により（１１０）面のピークが優勢となる。したがって、試料の表面を高圧ねじり加工することにより、特定の結晶方位に配向した領域を増加させることができる。最下段は、高圧ねじり加工した試料を、８００℃、５×１０−３Ｐａで１５分間熱処理した試料のＸ線回折結果を示す。熱処理により、（１１０）面のピークと、（１１０）面と等価な（２２０）面のピークのみが残り、それ以外のピークはほぼ消失している。したがって、試料の表面を高圧ねじり加工した後、熱処理を実施することにより、特定の結晶方位に配向した領域を更に増加させることができる。第３の方法によれば、表面のほぼ全ての金属が（１１０）面に配向した薄膜を安価かつ容易に製造することができる。 FIG. 16 shows the X-ray diffraction results of the thin film produced by the third method according to the present disclosure. The uppermost stage shows the same X-ray diffraction results of the sample after rolling as in the uppermost stage of FIG. The middle stage shows the X-ray diffraction results of the sample obtained by high-pressure twisting the surface of the rolled sample. The peak on the (110) plane becomes predominant due to the high-pressure twisting process. Therefore, by high-pressure twisting the surface of the sample, the region oriented in a specific crystal orientation can be increased. The bottom row shows the X-ray diffraction results of a sample obtained by heat-treating a high-pressure twisted sample at 800 ° C. and 5 × 10 -3 Pa for 15 minutes. By the heat treatment, only the peak of the (110) plane and the peak of the (220) plane equivalent to the (110) plane remain, and the other peaks are almost eliminated. Therefore, by performing heat treatment after high-pressure twisting the surface of the sample, the region oriented in a specific crystal orientation can be further increased. According to the third method, a thin film in which almost all the metals on the surface are oriented on the (110) plane can be produced inexpensively and easily.
以上、実施例をもとに本開示を説明した。この実施例は例示であり、それらの各構成要素や各処理プロセスの組合せにいろいろな変形例が可能なこと、またそうした変形例も本開示の範囲にあることは当業者に理解されるところである。 The present disclosure has been described above based on the examples. This embodiment is an example, and it will be understood by those skilled in the art that various modifications are possible for each of these components and combinations of each processing process, and that such modifications are also within the scope of the present disclosure. ..
１０・・・水素分離装置、２０・・・一次側配管、２２・・・外管、２４・・・内管、２６・・・原料気体供給流路、２８・・・原料気体排出流路、３０・・・二次側配管、３２・・・水素回収流路、４０・・・一次側ガスケット、４２・・・二次側ガスケット、５０・・・水素透過膜。 10 ... Hydrogen separator, 20 ... Primary side piping, 22 ... Outer pipe, 24 ... Inner pipe, 26 ... Raw material gas supply flow path, 28 ... Raw material gas discharge flow path, 30 ... Secondary side piping, 32 ... Hydrogen recovery flow path, 40 ... Primary side gasket, 42 ... Secondary side gasket, 50 ... Hydrogen permeable film.
Claims (14)
前記水素透過膜の表面に設けられた触媒層と、
を備え、
前記触媒層との境界面における前記水素透過膜の金属又は合金の所定比率以上が特定の結晶方位に配向した水素透過装置。 A hydrogen permeable membrane formed of pure metal or alloy,
A catalyst layer provided on the surface of the hydrogen permeable membrane and
With
A hydrogen permeation device in which a predetermined ratio or more of a metal or alloy of the hydrogen permeation membrane at the interface with the catalyst layer is oriented in a specific crystal orientation.
前記水素透過膜の表面に設けられた触媒層と、
を備え、
前記触媒層との境界面における前記水素透過膜の金属又は合金は、（１１０）面に配向した領域がその他の面に配向した領域よりも大きい水素透過装置。 A hydrogen permeable membrane formed of pure metal or alloy,
A catalyst layer provided on the surface of the hydrogen permeable membrane and
With
The metal or alloy of the hydrogen permeable membrane at the interface with the catalyst layer is a hydrogen permeation device in which the region oriented to the (110) plane is larger than the region oriented to the other plane.
前記水素透過膜の表面にパラジウムと銀の合金により形成された触媒層と、
を備え、
前記触媒層におけるパラジウムと銀の組成比は、一次側圧力が４００ｋＰａ、二次側圧力が１０３ｋＰａ、温度が４５０℃の条件下で前記水素透過膜の水素透過試験を実施した場合に透過流速が開始直後の透過流速から２０％減少する時点までの時間である２０％劣化時間ｔ０．２が４０時間以上となるような組成比である水素透過装置。 A hydrogen permeable membrane formed of pure metal or alloy,
A catalyst layer formed of an alloy of palladium and silver on the surface of the hydrogen permeable membrane,
With
Regarding the composition ratio of palladium and silver in the catalyst layer, the permeation flow velocity starts when the hydrogen permeation test of the hydrogen permeation film is carried out under the conditions of a primary pressure of 400 kPa, a secondary pressure of 103 kPa and a temperature of 450 ° C. A hydrogen permeation device having a composition ratio such that the 20% deterioration time t 0.2, which is the time from the permeation flow velocity immediately after the permeation to the time when it decreases by 20%, becomes 40 hours or more.
前記水素透過膜の表面の純金属又は合金のうち特定の結晶方位に配向した領域を増加させるステップと、
を備える水素透過装置の製造方法。 Steps to form a hydrogen permeable membrane from pure metal or alloy,
A step of increasing the region of the pure metal or alloy on the surface of the hydrogen permeable membrane oriented in a specific crystal orientation, and
A method for manufacturing a hydrogen permeation device.
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