JP5149050B2 - Hydrogen separator - Google Patents

Hydrogen separator Download PDF

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JP5149050B2
JP5149050B2 JP2008078891A JP2008078891A JP5149050B2 JP 5149050 B2 JP5149050 B2 JP 5149050B2 JP 2008078891 A JP2008078891 A JP 2008078891A JP 2008078891 A JP2008078891 A JP 2008078891A JP 5149050 B2 JP5149050 B2 JP 5149050B2
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hydrogen
permeable membrane
separation cylinder
hydrogen separation
gas
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JP2009234798A (en
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耕平 三矢
融 島森
義則 白崎
達也 常木
英人 黒川
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NGK Spark Plug Co Ltd
Tokyo Gas Co Ltd
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NGK Spark Plug Co Ltd
Tokyo Gas Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Description

本発明は、原料ガスから水素を選択して分離することができる水素分離装置に関する。   The present invention relates to a hydrogen separator that can selectively separate hydrogen from a source gas.

水素の工業的製造方法の一つとして、炭化水素ガスの水蒸気改質法が知られており、この水蒸気改質法では、通常、粒状等の改質触媒を充填した改質器が用いられる。
ところが、改質器で得られる改質ガスには、主成分である水素のほか、ＣＯ、ＣＯ2等の副生成分や余剰Ｈ2Ｏが含まれているので、改質ガスを、例えば燃料電池にそのまま用いたのでは電池性能を阻害してしまう。 As one of the industrial methods for producing hydrogen, a steam reforming method of hydrocarbon gas is known. In this steam reforming method, a reformer filled with a reforming catalyst such as a granule is usually used.
However, the reformed gas obtained from the reformer contains by-products such as CO and CO 2 and surplus H 2 O in addition to hydrogen as the main component. If it is used as it is for a battery, battery performance will be impaired.

つまり、燃料電池のうち、リン酸形燃料電池で用いる水素ガス中のＣＯは１％（ｖｏｌ％）程度、固体高分子形燃料電池では１００ｐｐｍ（ｖｏｌｐｐｍ）程度が限度であり、これらを超えると電池性能が著しく劣化するため、それら副生成分は燃料電池へ導入する前に除去する必要がある。   That is, of the fuel cells, CO in hydrogen gas used in phosphoric acid fuel cells is limited to about 1% (vol%), and in solid polymer fuel cells, the limit is about 100 ppm (vol ppm). Since the performance deteriorates significantly, these by-products need to be removed before being introduced into the fuel cell.

この対策として、改質器による改質ガスの生成と該改質ガスの精製とを一つの装置で行えるように一体化したメンブレンリアクタが開発されている（特許文献１参照）。
また、近年では、メンブレンリアクタの（複雑な構造に起因する）問題点を解決するために、水素透過膜の支持体として改質触媒兼支持体を用いた試験管状の水素分離筒を備えるとともに、水素分離筒を固定する取付金具等を備えた水素分離装置が提案されている（特許文献２参照）。 As a countermeasure, a membrane reactor has been developed in which the generation of the reformed gas by the reformer and the purification of the reformed gas can be performed with one apparatus (see Patent Document 1).
In recent years, in order to solve the problems of the membrane reactor (due to the complicated structure), a hydrogen separation membrane having a test tube as a support for the hydrogen permeable membrane is used as a support for the hydrogen permeable membrane. There has been proposed a hydrogen separator provided with a mounting bracket or the like for fixing a hydrogen separator cylinder (see Patent Document 2).

この引用文献２の技術では、水素分離筒は例えば筒状の容器（反応管）内に収納され、その反応管内にて水素が捕集されるが、水素透過膜は水素分離筒の表面に形成されているので、反応管等から脱落した金属微粒子などによって、水素透過膜が破損することがあった。つまり、反応管等から脱落した金属微粒子などの異物が水素透過膜に付着すると、膜成分との反応によって、水素透過膜に孔があいたり、水素透過膜の性能が低下するという問題があった。   In the technique of this reference 2, the hydrogen separation cylinder is accommodated in, for example, a cylindrical container (reaction tube), and hydrogen is collected in the reaction tube, but the hydrogen permeable membrane is formed on the surface of the hydrogen separation cylinder. As a result, the hydrogen permeable membrane may be damaged by metal fine particles dropped from the reaction tube or the like. In other words, when foreign matters such as metal fine particles dropped from the reaction tube adhere to the hydrogen permeable membrane, there is a problem that the reaction with the membrane component causes a hole in the hydrogen permeable membrane or the performance of the hydrogen permeable membrane decreases. .

この対策として、水素分離筒の表面（即ち水素透過膜の表面）を、多孔質焼結体で覆った技術が提案されている（特許文献３参照）。この技術は、多孔質の金属焼結体やセラミック焼結体で水素分離筒の表面を覆ったり、水素分離筒を所定の懸濁溶液に漬けた後に焼成し表面に多孔質焼成層を形成するものである。
特開２００４−０１９８７９号公報 特開２００４−１４９３３２号公報 特開２００７−９０２９５号公報 As a countermeasure, a technique has been proposed in which the surface of the hydrogen separation cylinder (that is, the surface of the hydrogen permeable membrane) is covered with a porous sintered body (see Patent Document 3). In this technique, the surface of the hydrogen separation cylinder is covered with a porous metal sintered body or ceramic sintered body, or the hydrogen separation cylinder is immersed in a predetermined suspension solution and fired to form a porous fired layer on the surface. Is.
JP 2004-019879 A JP 2004-149332 A JP 2007-90295 A

しかしながら、上述した引用文献３の技術では、例えば焼結されたセラミック多孔体を水素分離筒の外周面に沿って固定することは、実際には難しいという問題がある。
また、水素分離筒の表面に多孔質の焼結層を形成する場合には、水素分離筒の表面は微粉末であるので、先に焼成していなければ懸濁した溶液に浸けることは難しく、また、先に焼成するにしても、温度を上げる際に、水素透過膜に損傷を与える恐れがある。
更に粉末を焼成して多孔体を作成した場合には、焼結が不十分であったり、周囲との接触で崩れた場合、それ自体が飛散し、水素透過膜に損傷を与える恐れがある。 However, the technique of the above cited reference 3 has a problem that it is actually difficult to fix the sintered ceramic porous body along the outer peripheral surface of the hydrogen separation cylinder, for example.
In addition, when forming a porous sintered layer on the surface of the hydrogen separation cylinder, the surface of the hydrogen separation cylinder is a fine powder, so it is difficult to immerse it in a suspended solution unless it has been fired first. Even if the baking is performed first, the hydrogen permeable membrane may be damaged when the temperature is raised.
Further, when the porous body is made by firing the powder, if the sintering is insufficient or if the porous body collapses due to contact with the surroundings, the powder itself may scatter and damage the hydrogen permeable membrane.

本発明は、上述した課題を解決するためになされたものであり、その目的は、外部からの異物が水素透過膜に付着することを防止するともに、その製造が容易で、しかも、水素透過膜を損傷する恐れのない水素分離装置を提供することである。   The present invention has been made in order to solve the above-described problems. The object of the present invention is to prevent foreign substances from adhering to the hydrogen permeable membrane, and to easily manufacture the hydrogen permeable membrane. It is an object of the present invention to provide a hydrogen separator that does not cause damage.

（１）請求項１の発明は、金属製の反応管内に収容される水素分離筒であって、原料ガスから水素を選択して分離する水素透過膜が外側に形成された水素分離筒を備えた水素分離装置において、前記水素透過膜の外側の表面を覆うように、前記反応管からの微粒子が前記水素透過膜に到ることを防止する保護部材を配置するとともに、前記保護部材は、セラミックの繊維からなる糸を編み上げた筒状体であって、水素ガスの透過量が、８０％以上であることを特徴とする。 (1) The invention of claim 1 is a hydrogen separation cylinder accommodated in a metal reaction tube, comprising a hydrogen separation cylinder on the outside of which a hydrogen permeable membrane for selecting and separating hydrogen from a source gas is formed. In the hydrogen separator, a protective member for preventing fine particles from the reaction tube from reaching the hydrogen permeable membrane is disposed so as to cover the outer surface of the hydrogen permeable membrane, and the protective member is made of ceramic. It is a cylindrical body knitted from yarn made of mulberry fibers, and the hydrogen gas permeation amount is 80% or more.

本発明は、金属製の反応管内に収容される水素分離筒（従ってその表面の水素透過膜）を覆うように、通気性を有し且つ微粒子の通過を阻止する保護部材が設けられているので、水素ガスの透過を損なうことなく、水素透過膜の表面に（水素透過膜を損なう）金属微粒子等が付着することを好適に防止できる。そのため、水素透過膜に孔があいたり、水素透過膜の性能が低下することを防止できる。 Since the present invention is provided with a protective member having air permeability and preventing passage of fine particles so as to cover a hydrogen separation cylinder (and hence a hydrogen permeable membrane on the surface) accommodated in a metal reaction tube . Further, it is possible to suitably prevent metal fine particles or the like (which impairs the hydrogen permeable film) from adhering to the surface of the hydrogen permeable film without impairing the permeation of hydrogen gas. Therefore, it is possible to prevent a hole from being formed in the hydrogen permeable membrane and a decrease in the performance of the hydrogen permeable membrane.

つまり、保護部材には、一種のふるい（篩）として、ガスの通過は十分に可能であるが、微粒子の通過を阻止できる程度の細孔や間隙が形成されているので、ガスの通過と微粒子の通過の阻止との両立が可能である。   That is, as a kind of sieve (sieving), the protective member is sufficiently capable of passing gas, but has pores and gaps that can prevent passage of fine particles. It is possible to prevent the passage of

しかも、本発明では、保護部材は、セラミックの繊維からなる糸を編み上げた筒状体で、従来の様な高温での熱処理が不要であり、水素透過膜に悪影響を与えることがなく、水素分離筒の外側に嵌め込むだけで、容易に取り付けが可能である。
また、この保護部材は、硬質のセラミック焼結体ではなく、繊維の筒状体であるので、水素透過膜より十分な柔軟性を有しており、よって、水素透過膜を破損し難いという利点がある。
更に、水素ガスは、セラミックの繊維からなる糸を編み上げた筒状体の隙間等を通過できるが、その隙間は微細であるので大きな寸法の微粒子は通過できない。 Moreover, in the present invention, the protective member is a cylindrical body with braided yarn consisting of fibers of ceramic, it is unnecessary to heat treatment in a conventional manner, such high temperatures, without adversely affecting the hydrogen-permeable membrane, the hydrogen It can be easily attached by simply fitting it to the outside of the separation cylinder.
In addition, since this protective member is not a hard ceramic sintered body but a cylindrical body of fibers, it has sufficient flexibility than the hydrogen permeable membrane, and therefore, the advantage that the hydrogen permeable membrane is difficult to break. There is.
Furthermore, hydrogen gas can pass through the gap between the yarn braided tubular body made of ceramic fiber or the like, the gap is fine for large size because it is finely that can not be passed.

また、保護部材を固定する場合には、Ｎｉ線やＰｔ線で保護部材の外表面を巻いて固定でき、例えば水素分離筒が固定される根元部分にて、保護部材の外周面を巻き付けて固定できる。なお、Ｐｔ線やＮｉ線の様な金属線以外にも、膨張黒鉛のリングをスリーブの上から押圧して固定することも可能である。   In addition, when fixing the protective member, the outer surface of the protective member can be wound and fixed with Ni wire or Pt wire. For example, the outer peripheral surface of the protective member is wound and fixed at the root portion where the hydrogen separation cylinder is fixed. it can. In addition to metal wires such as Pt wires and Ni wires, it is also possible to press and fix an expanded graphite ring from above the sleeve.

更に、保護部材が通過を阻止できる微粒子としては、０．５μｍ以上の微粒子が挙げられる。ここで、阻止できる微粒子の寸法とは、微粒子における最大の寸法を示している（以下同様）。
（２）請求項２の発明では、前記保護部材を形成する繊維は、直径０．５〜１００μｍである。さらに好ましくは１〜１０μｍである。
直径が０．５μｍ未満の場合は、シートやスリーブの作製が難しく、１００μmを上回る
場合は、シートやスリーブの目が粗くなり、微粒子が透過しやすくなる。
（３）請求項３の発明は、金属製の反応管内に収容される水素分離筒であって、原料ガスから水素を選択して分離する水素透過膜が外側に形成された水素分離筒を備えた水素分離装置において、前記水素透過膜の外側の表面を覆うように、前記反応管からの微粒子が前記水素透過膜に到ることを防止する保護部材を配置するとともに、前記保護部材は、セラミックの繊維からなる糸を編み上げた筒状体であって、通気性を有するとともに、０．５μｍ以上の微粒子が透過できない構造を有することを特徴とする。 Furthermore, the fine particles that can prevent the protective member from passing include fine particles having a size of 0.5 μm or more. Here, the size of the fine particles that can be blocked indicates the maximum size of the fine particles (the same applies hereinafter).
(2) In invention of Claim 2, the fiber which forms the said protection member is 0.5-100 micrometers in diameter. More preferably, it is 1-10 micrometers.
When the diameter is less than 0.5 μm, it is difficult to produce a sheet or a sleeve. When the diameter is more than 100 μm, the eyes of the sheet or sleeve become rough, and the fine particles easily pass through.
(3) The invention of claim 3 is a hydrogen separation cylinder accommodated in a metal reaction tube, comprising a hydrogen separation cylinder formed on the outside with a hydrogen permeable membrane for selecting and separating hydrogen from the source gas. In the hydrogen separator, a protective member for preventing fine particles from the reaction tube from reaching the hydrogen permeable membrane is disposed so as to cover the outer surface of the hydrogen permeable membrane, and the protective member is made of ceramic. It is characterized in that it is a tubular body knitted from yarns made of the above fibers, has air permeability, and has a structure in which fine particles of 0.5 μm or more cannot permeate.

本発明は、金属製の反応管内に収容される水素分離筒（従ってその表面の水素透過膜）を覆うように、通気性を有し且つ微粒子の通過を阻止する保護部材が設けられているので、水素ガスの透過を損なうことなく、水素透過膜の表面に（水素透過膜を損なう）金属微粒子が付着することを好適に防止できる。そのため、水素透過膜に孔があいたり、水素透過膜の性能が低下することを防止できる。 Since the present invention is provided with a protective member having air permeability and preventing passage of fine particles so as to cover a hydrogen separation cylinder (and hence a hydrogen permeable membrane on the surface) accommodated in a metal reaction tube . Further, it is possible to suitably prevent metal fine particles from adhering to the surface of the hydrogen permeable film (which damages the hydrogen permeable film) without impairing the permeation of hydrogen gas. Therefore, it is possible to prevent a hole from being formed in the hydrogen permeable membrane and a decrease in the performance of the hydrogen permeable membrane.

つまり、保護部材には、一種のふるい（篩）として、ガスの通過は十分に可能であるが、０．５μｍ以上の微粒子の通過を阻止できる程度の細孔や間隙が形成されているので、ガスの通過と微粒子の通過の阻止との両立が可能である。   That is, as a kind of sieve (sieving), the protective member is sufficiently capable of passing gas, but has pores and gaps that can prevent passage of fine particles of 0.5 μm or more. Both passage of gas and prevention of passage of fine particles are possible.

＜以下、本発明の水素分離装置及び水素製造装置の各構成について説明する＞
・前記原料ガスとしては、都市ガス等の炭化水素ガスと水蒸気の混合ガス等が挙げられる。 <Hereinafter, each configuration of the hydrogen separation apparatus and the hydrogen production apparatus of the present invention will be described>
-As said source gas, the mixed gas etc. of hydrocarbon gas, such as city gas, and water vapor | steam are mentioned.

・前記水素分離筒としては、（改質触媒兼支持体である）多孔質支持管の表面に水素透過膜が形成された筒状体や、多孔質支持管の表面に（金属の拡散を防止する）バリア層が形成され、更にバリア層の表面に水素透過膜が形成された筒状体が挙げられる。   -As the hydrogen separation cylinder, a cylindrical body in which a hydrogen permeable membrane is formed on the surface of a porous support pipe (which is a reforming catalyst and support), or a surface of the porous support pipe (to prevent metal diffusion) And a cylindrical body in which a barrier layer is formed and a hydrogen permeable film is further formed on the surface of the barrier layer.

このうち、多孔質支持管を構成する材料としては、例えばニッケルとイットリア安定化ジルコニアの混合物の焼結体、ニッケルとイットリア安定化ジルコニアの混合物を主体とする焼結体（Ｎｉ−ＹＳＺサーメット等）、その他、支持体としての機能と改質触媒としての機能の両機能を合わせ有する多孔質セラミックス、多孔質サーメットなどが挙げられる。   Among these, as a material constituting the porous support tube, for example, a sintered body of a mixture of nickel and yttria stabilized zirconia, a sintered body mainly composed of a mixture of nickel and yttria stabilized zirconia (Ni-YSZ cermet, etc.) Other examples include porous ceramics and porous cermets having both the function as a support and the function as a reforming catalyst.

水素透過膜としては、例えばＰｄ膜やＰｄ合金膜などの金属膜が挙げられる。
バリア層の構成材料としては、例えばジルコニア、安定化ジルコニア、部分安定化ジルコニア、アルミナ、マグネシア、もしくはそれらの材料の混合物もしくは化合物を用いることができる。 Examples of the hydrogen permeable film include metal films such as a Pd film and a Pd alloy film.
As a constituent material of the barrier layer, for example, zirconia, stabilized zirconia, partially stabilized zirconia, alumina, magnesia, or a mixture or compound of these materials can be used.

・保護部材の繊維の材質としては、水素分離装置や水素製造装置を作動させる条件、即ち水素雰囲気や作動温度の条件にて劣化し難いものが好適である。例えば前記セラミックの繊維としては、アルミナ−シリカなどの繊維が挙げられる。 - The material of the fibers of the protection member, the conditions for operating the hydrogen separator and the hydrogen production device, i.e. those hardly deteriorated under a hydrogen atmosphere or in the operating temperature conditions are preferred. For example As the ceramic fibers, alumina - Ru include fibers such as silica.

なお、保護部材の形状としては、水素分離筒や容器等の形状に合わせて作製すればよい。例えば水素分離筒が試験管のような形状（一端側が開放され他端側が閉塞された筒形状）であれば、保護部材の形状の試験管のような形状のものを採用できる。   In addition, what is necessary is just to produce as a shape of a protection member according to shapes, such as a hydrogen separation cylinder and a container. For example, if the hydrogen separation cylinder has a shape like a test tube (a cylinder shape in which one end side is opened and the other end side is closed), a shape like a test tube in the shape of a protective member can be adopted.

以下、本発明の最良の実施形態について説明する。
［第１実施形態］
ここでは、燃料電池に燃料ガス（水素ガス）を供給する水素分離装置及び水素製造装置について説明する。 Hereinafter, the best embodiment of the present invention will be described.
[First Embodiment]
Here, a hydrogen separator and a hydrogen production apparatus that supply fuel gas (hydrogen gas) to the fuel cell will be described.

ａ）まず、本実施形態の水素分離装置について説明する。
図１に示す様に、本実施形態の水素分離装置（水素分離モジュール）１は、一端が閉塞された試験管の形状の水素分離筒３と、水素分離筒３の開放端側が挿入された筒状の取付金具５と、水素分離筒３の外周面と取付金具５の内周面との間に配置された円筒形のシール部材７と、水素分離筒３に外嵌されてシール部材７の先端側（同図左側）を押圧する円筒形の押圧金具９と、押圧金具９に外嵌されて取付金具５に螺合する筒状の固定金具１１と、水素分離筒３の外側表面を覆う保護スリーブ（保護部材）１３とを備えている。 a) First, the hydrogen separator according to this embodiment will be described.
As shown in FIG. 1, a hydrogen separation device (hydrogen separation module) 1 of this embodiment includes a hydrogen separation cylinder 3 in the shape of a test tube closed at one end, and a cylinder into which the open end side of the hydrogen separation cylinder 3 is inserted. Of the cylindrical mounting member 5, a cylindrical sealing member 7 disposed between the outer peripheral surface of the hydrogen separation cylinder 3 and the inner peripheral surface of the mounting bracket 5, Covers the outer surface of the hydrogen separation cylinder 3, a cylindrical pressing fitting 9 that presses the distal end side (left side of the figure), a cylindrical fixing fitting 11 that is externally fitted to the pressing fitting 9 and is screwed into the mounting fitting 5. And a protective sleeve (protective member) 13.

前記水素分離筒３は、その軸中心の中心孔１４に導入された原料ガス（例えばメタンなどの炭化水素ガスと水蒸気の混合ガス）から、水素を選択的に分離して、水素分離筒３の外周側に供給する部材である。この水素分離筒３は、一端が閉塞された試験管状をした（改質触媒兼支持体である）多孔質支持管１５と、多孔質支持管１５の外側表面を覆うバリア層１９と、バリア層１９の外側表面を覆う水素透過膜２１とから構成されている。   The hydrogen separation cylinder 3 selectively separates hydrogen from a raw material gas (for example, a mixed gas of hydrocarbon gas such as methane and water vapor) introduced into the central hole 14 at the axial center of the hydrogen separation cylinder 3. It is a member supplied to the outer peripheral side. This hydrogen separation cylinder 3 has a test tube with one end closed (a reforming catalyst and support), a porous support tube 15, a barrier layer 19 covering the outer surface of the porous support tube 15, and a barrier layer And a hydrogen permeable membrane 21 that covers the outer surface of 19.

このうち、多孔質支持管１５は、改質触媒としての役割と水素透過膜２１等を支持する役割とを有する通気性を有する試験管状のセラミックス製の支持体であり、この多孔質支持管１５では、原料ガスを水蒸気改質して改質ガスを生成する。   Among these, the porous support tube 15 is a gas-permeable test tube ceramic support having a role as a reforming catalyst and a role of supporting the hydrogen permeable membrane 21 and the like. Then, the reformed gas is generated by steam reforming the raw material gas.

水素透過膜２１は、多孔質支持管１５内で改質された改質ガスから水素を選択的に透過して精製する機能を有する金属製の薄膜である。
バリア層１９は、多孔質支持管１５の金属成分（例えばＮｉ）と水素透過膜２１の成分（例えばＰｄ）とが互いに入り込む（拡散する）ことにより、水素透過膜２１の水素透過性能が劣化することを防止するためのセラミックス製の多孔質層（相互拡散防止層）である。 The hydrogen permeable membrane 21 is a metal thin film having a function of selectively permeating and purifying hydrogen from the reformed gas reformed in the porous support tube 15.
In the barrier layer 19, the metal component (for example, Ni) of the porous support tube 15 and the component (for example, Pd) of the hydrogen permeable membrane 21 enter (diffuse) each other, so that the hydrogen permeable performance of the hydrogen permeable membrane 21 deteriorates. This is a ceramic porous layer (interdiffusion prevention layer) for preventing this.

また、前記取付金具５は、水素分離装置１の基部を構成する例えばステンレス製の筒状金具であり、その先端側より、外周にねじ部２３を有する先端側筒状部２５と、外周側に環状に張り出す鍔部２７と、（原料ガスを供給する配管等が接続される）基端側筒状部２９とを備えている。   Further, the mounting bracket 5 is, for example, a stainless steel cylindrical bracket that constitutes the base of the hydrogen separation device 1. From the distal end side, a distal end side cylindrical portion 25 having a screw portion 23 on the outer periphery, and an outer peripheral side. An eaves portion 27 that projects in an annular shape and a proximal-side cylindrical portion 29 (to which a pipe or the like for supplying a raw material gas is connected) are provided.

この取付金具５の軸中心には、原料ガスの流路となる貫通孔３１が形成され、貫通孔３１には、水素分離筒３の基端側（同図右側）の端部が収容されている。詳しくは、鍔部２７内側の先端側の角部には、先端側筒状部２５と所定の間隔を空けて、段状に切り欠いた凹部３３が形成され、この凹部３３に水素分離筒３の端部が内嵌している。   A through hole 31 serving as a raw material gas flow path is formed at the axial center of the mounting bracket 5, and the end of the base end side (right side of the figure) of the hydrogen separation cylinder 3 is accommodated in the through hole 31. Yes. Specifically, a concave portion 33 that is notched in a step shape is formed at a corner portion on the distal end side inside the flange portion 27 at a predetermined interval from the distal tubular portion 25, and the hydrogen separation cylinder 3 is formed in the concave portion 33. The end of is fitted.

前記シール部材７は、膨張黒鉛からなる円筒状の気密部材であり、取付金具５の先端側筒状部２５の内周面と水素分離筒３の外周面との間の空間３５内にて、押圧金具９と隣接して配置されている。なお、シール部材７は、先端側（ガスの上流側）に配置された第１シール部材３７と、後端側に配置された第２シール部材３９とから構成されている。   The seal member 7 is a cylindrical airtight member made of expanded graphite, and in a space 35 between the inner peripheral surface of the distal end side tubular portion 25 of the mounting bracket 5 and the outer peripheral surface of the hydrogen separation tube 3, It is arranged adjacent to the pressing fitting 9. The seal member 7 includes a first seal member 37 disposed on the front end side (upstream side of the gas) and a second seal member 39 disposed on the rear end side.

前記押圧金具９は、円筒形状の例えばステンレス製の筒状金具であり、取付金具５の先端側筒状部２５の内周面と水素分離筒３の外周面との間に形成された筒状の空間３５内にて、シール部材７と隣接して配置されている。   The pressing metal 9 is a cylindrical metal fitting made of, for example, stainless steel, and is formed between the inner peripheral surface of the distal end side cylindrical portion 25 of the mounting bracket 5 and the outer peripheral surface of the hydrogen separation cylinder 3. Is disposed adjacent to the seal member 7 in the space 35.

前記固定金具１１は、例えばステンレス製の筒状金具であり、環状の押圧板４１と内周面にねじ部４３を有する筒状部４５とを備えている。従って、この固定金具１１のねじ部４３と取付金具５のねじ部２３を螺合させて締め付けることにより、押圧金具９を介してシール部材７を、基端側に押圧することができる。   The fixing metal fitting 11 is a cylindrical metal fitting made of stainless steel, for example, and includes an annular pressing plate 41 and a cylindrical portion 45 having a screw portion 43 on the inner peripheral surface. Therefore, the sealing member 7 can be pressed to the proximal end side via the pressing fitting 9 by screwing and tightening the screw portion 43 of the fixing fitting 11 and the screw portion 23 of the mounting fitting 5.

特に、前記保護スリーブ１３は、収納容器（反応管）５３（図３参照）から脱落し水素分離筒３の周囲に浮遊する金属微粒子等の異物が、水素分離筒３に付着することを防止し、且つ、水素ガスが透過可能な通気性を有する筒状部材である。   In particular, the protective sleeve 13 prevents foreign substances such as metal fine particles that have fallen out of the storage container (reaction tube) 53 (see FIG. 3) and floated around the hydrogen separation cylinder 3 from adhering to the hydrogen separation cylinder 3. And a cylindrical member having air permeability through which hydrogen gas can permeate.

詳しくは、保護スリーブ１３は、例えばアルミナ等の繊維からなる糸を筒状に編み上げた編み物により構成されたものであり、固定金具１１の先端側（図１左側）から突出する水素分離筒３の外側表面の全体を、隙間無く覆っている。 Specifically, the protective sleeve 13, for example, has been constructed by knitting braided yarn consisting of fibers such as alumina to the cylindrical hydrogen separator tube 3 projecting from the front end side of the fixing bracket 11 (Fig. 1 left) The entire outer surface of the cover is covered without any gaps.

なお、長繊維でできた糸を織って作られた保護スリーブ１３の方が、繊維自体が崩れて飛散するということが起こりにくいという利点がある。
この保護スリーブ１３は、水素分離筒３から脱落しないように、複数箇所にて金属ワイヤ４７にて締め付けられており、保護スリーブ１３の軸方向の開放された一端（図１右側）は、固定金具１１と水素分離筒３の間の間隙に差し込まれて押圧金具９のテーパ部分にまで達しており、他端は金属ワイヤ４７により締め付けられて閉塞されている。なお、図２では、保護スリーブ１３の開放された一端が、固体金具１１の端面（同図左側）に密接した例を示している。 Note that the protective sleeve 13 made by weaving yarn made of long fibers has the advantage that the fibers themselves are less likely to collapse and scatter.
The protective sleeve 13 is fastened with metal wires 47 at a plurality of locations so as not to drop off from the hydrogen separation cylinder 3, and one end (right side in FIG. 1) of the protective sleeve 13 in the axial direction is fixed metal fittings. 11 is inserted into the gap between the hydrogen separation cylinder 3 and reaches the taper portion of the press fitting 9, and the other end is clamped and closed by a metal wire 47. FIG. 2 shows an example in which the open end of the protective sleeve 13 is in close contact with the end face (the left side of the figure) of the solid metal fitting 11.

また、保護スリーブ１３は、水素分離筒３で分離されて外周側に供給される水素が十分に透過可能なガス透過性能を有している。具体的には、保護スリーブ１３を取り付けた場合でも、（保護スリーブ１３が無い場合と比べて）ガスの透過量は２０％以上低下しないガス透過性能、つまり水素ガスの透過量が８０％以上のガス透過性能を有している。更に、保護スリーブ１３の繊維等の隙間は、例えば０．５μｍ以上の微粒子が通過できない程度に、十分に小さく設定されている。
なお、前記図１に示す様に、本実施形態の水素分離装置１の内部（詳しくは水素分離筒３の中心孔１４）には、内挿管５０が配置されている。この内挿管５０は、原料ガスを、水素分離装置１の基端側から水素分離筒３の先端側に供給する部材であり、反応後のオフガス（ＣＯ、ＣＯ2、Ｈ2、メタン、水蒸気）は、内挿管５０の外周に沿って水素分離装置１の基端側から排出される。 Further, the protective sleeve 13 has a gas permeation performance that can sufficiently permeate hydrogen separated by the hydrogen separation cylinder 3 and supplied to the outer peripheral side. Specifically, even when the protective sleeve 13 is attached, the gas permeation performance does not decrease by 20% or more (compared to the case without the protective sleeve 13), that is, the hydrogen gas permeation amount is 80% or more. Has gas permeability. Furthermore, the gaps such as the fibers of the protective sleeve 13 are set to be sufficiently small so that, for example, fine particles of 0.5 μm or more cannot pass through.
As shown in FIG. 1, an intubation tube 50 is disposed inside the hydrogen separation apparatus 1 of the present embodiment (specifically, the center hole 14 of the hydrogen separation cylinder 3). This inner tube 50 is a member that supplies the raw material gas from the base end side of the hydrogen separation device 1 to the front end side of the hydrogen separation cylinder 3, and is an off-gas after reaction (CO, CO 2 , H 2 , methane, water vapor). Is discharged from the proximal end side of the hydrogen separator 1 along the outer periphery of the inner intubation 50.

ｂ）次に、水素分離装置１が取り付けられる水素分離システム（水素製造装置）について説明する。
図３に示す様に、水素製造装置５１は、上述した水素分離装置１が、例えばＳＵＳ４０５、ＳＵＳ３１６、ＳＵＳ３０４、ＳＵＳ４３０等のステンレスや、コバール、インコネル、パーマロイなど、金属製の筒状の反応管５３内に、複数本（例えば３本）収容されて固定されたものである。 b) Next, a hydrogen separation system (hydrogen production apparatus) to which the hydrogen separation apparatus 1 is attached will be described.
As shown in FIG. 3, in the hydrogen production apparatus 51, the hydrogen separation apparatus 1 described above is made of a metal cylindrical reaction tube 53 such as stainless steel such as SUS405, SUS316, SUS304, or SUS430, or Kovar, Inconel, Permalloy, or the like. A plurality (for example, three) are accommodated and fixed inside.

前記反応管５３は、円筒状の外周壁５５と、外周壁５５の軸方向の一方を塞ぐ基板５７と、他方を塞ぐ蓋板５９とを備えており、各水素分離装置１は、この基板５７を貫く様に配置されている。詳しくは、各水素分離装置１は、各取付金具５の鍔部２７にて、例えば溶接等により、基板５７に固定されている（図１参照）。   The reaction tube 53 includes a cylindrical outer peripheral wall 55, a substrate 57 that closes one of the outer peripheral walls 55 in the axial direction, and a lid plate 59 that closes the other. It is arranged to penetrate. Specifically, each hydrogen separator 1 is fixed to the substrate 57 by, for example, welding or the like at the flange portion 27 of each mounting bracket 5 (see FIG. 1).

また、取付金具５の下部には、原料ガスを供給するための配管６１が、ナット６３により取り付けられている。更に、反応管５３の外周壁５５には、水素を取り出す水素取出孔６５が設けられている。   In addition, a pipe 61 for supplying a source gas is attached to the lower part of the mounting bracket 5 with a nut 63. Furthermore, a hydrogen extraction hole 65 for taking out hydrogen is provided in the outer peripheral wall 55 of the reaction tube 53.

従って、この水素製造装置５１では、水素分離装置１の取付金具５の下側に取り付けられた配管６１から、内挿管５０を介して水素分離筒３の内部に原料ガスが供給されると、水素分離筒３により水素が分離され、その外周側より保護スリーブ１３を介して反応管５３内に水素が供給される。そして、反応管５３内に充満した水素は、水素取出孔６５を介して外部に取り出される。   Therefore, in this hydrogen production apparatus 51, when the source gas is supplied from the pipe 61 attached to the lower side of the mounting bracket 5 of the hydrogen separation apparatus 1 to the inside of the hydrogen separation cylinder 3 through the inner tube 50, Hydrogen is separated by the separation cylinder 3, and hydrogen is supplied into the reaction tube 53 through the protective sleeve 13 from the outer peripheral side. Then, the hydrogen filled in the reaction tube 53 is taken out through the hydrogen take-out hole 65.

この水素取出孔６５から取り出された水素は、図示しない燃料電池に供給されて発電が行われる。
ｃ）次に、本実施形態の水素分離装置１の製造方法について説明する。
＜水素分離筒３の製造方法＞
例えば酸化ニッケル６０質量部と、イットリア８モル％を固溶させたジルコニア４０質量部（８ＹＳＺ）とを混合する。更に造孔剤として黒鉛粉（又はコンスターチ）を混合して混合材を作製する。 The hydrogen taken out from the hydrogen take-out hole 65 is supplied to a fuel cell (not shown) to generate power.
c) Next, the manufacturing method of the hydrogen separator 1 of this embodiment is demonstrated.
<Method for Producing Hydrogen Separation Tube 3>
For example, 60 parts by mass of nickel oxide and 40 parts by mass (8YSZ) of zirconia in which 8 mol% of yttria is dissolved are mixed. Further, graphite powder (or starch) is mixed as a pore forming agent to prepare a mixed material.

そして、この混合材を用い、押出成形によって、有底円筒管を成形する。
次に、有底円筒管を乾燥した後に、脱脂処理を行い、１４００℃で１時間焼成して、ＮｉＯ−ＹＳＺで形成された多孔質支持管１５を作製する。 And a bottomed cylindrical tube is shape | molded by extrusion molding using this mixed material.
Next, after the bottomed cylindrical tube is dried, it is degreased and fired at 1400 ° C. for 1 hour to produce a porous support tube 15 formed of NiO—YSZ.

これとは別に、８ＹＳＺとバインダとエタノールを添加して、スラリーを調製する。
次に、このスラリーを、ディップコート法（又はスプレー吹き付け法、印刷法等）により、多孔質支持管１５の表面上に塗布してコート層を形成する。 Separately from this, 8YSZ, a binder and ethanol are added to prepare a slurry.
Next, this slurry is applied onto the surface of the porous support tube 15 by a dip coating method (or spray spraying method, printing method, etc.) to form a coating layer.

次に、このコート層を１３００℃で加熱処理して焼き付けし、バリア層１９を形成する。
このバリア層１９により被覆された多孔質支持管１５を、エタノールで３０分間超音波洗浄し、１２０℃で乾燥させる。 Next, this coat layer is baked by heat treatment at 1300 ° C. to form the barrier layer 19.
The porous support tube 15 covered with the barrier layer 19 is ultrasonically cleaned with ethanol for 30 minutes and dried at 120 ° C.

次に、バリア層１９を覆う様に、無電解メッキ法（又は真空蒸着法、スパッタリング法等）により、Ｐｄ等による水素透過膜２１を形成する。
次に、水素雰囲気下にて６００℃で３時間還元処理を施し、これにより、水素分離筒３を完成する。
＜シール部材７の製造方法＞
第１シール部材３７を製造する場合には、膨張黒鉛製のシートを環状に切断し、その環状のシートを各貫通孔を合わせるようにして積層する。 Next, a hydrogen permeable film 21 made of Pd or the like is formed by an electroless plating method (or a vacuum deposition method, a sputtering method, or the like) so as to cover the barrier layer 19.
Next, reduction treatment is performed at 600 ° C. for 3 hours under a hydrogen atmosphere, thereby completing the hydrogen separation cylinder 3.
<Method for Manufacturing Seal Member 7>
When the first seal member 37 is manufactured, the expanded graphite sheet is cut into an annular shape, and the annular sheet is laminated so that the respective through holes are aligned.

次に、この積層体を、濃硫酸、硝酸などの酸化剤により酸化処理することによって、膨張黒鉛内の層間距離を膨張させる。その後、この膨張黒鉛を、所定密度範囲となるように、プレス成形により負荷・圧縮する。   Next, this laminate is oxidized with an oxidizing agent such as concentrated sulfuric acid or nitric acid to expand the interlayer distance in the expanded graphite. Thereafter, the expanded graphite is loaded and compressed by press molding so as to be in a predetermined density range.

第２シール部材３９を製造する場合には、同様な膨張黒鉛製のシートを巻き付けることにより、筒状の積層体を形成する。
次に、この積層体を、濃硫酸、硝酸などの酸化剤により酸化処理することによって、膨張黒鉛を同様に膨張させる。その後、この膨張黒鉛を、同様に負荷・圧縮する。
＜水素分離装置１の組付方法＞
取付金具５の貫通孔３１に、第２シール材３９、第１シール材３７、押圧金具９の順で内嵌する。 When manufacturing the 2nd sealing member 39, a cylindrical laminated body is formed by winding the sheet | seat made from the same expanded graphite.
Next, the expanded graphite is similarly expanded by oxidizing the laminate with an oxidizing agent such as concentrated sulfuric acid or nitric acid. Thereafter, the expanded graphite is similarly loaded and compressed.
<Assembly method of hydrogen separator 1>
The second sealing material 39, the first sealing material 37, and the pressing metal fitting 9 are fitted in the through hole 31 of the mounting metal fitting 5 in this order.

次に、水素分離筒３の開放端側を、押圧金具９の貫通孔、第１シール材３７、第２シール材３９を通す様に挿入し、水素分離筒３の端部を取付金具５の凹部３３に嵌める。
次に、水素分離筒３の先端側より固定金具１１を外嵌し、固定金具１１のねじ部４３と取付金具５のねじ部２３を螺合し、固定金具１１により押圧金具９を基端側に締め付ける。 Next, the open end side of the hydrogen separation cylinder 3 is inserted so as to pass through the through hole of the pressing fitting 9, the first sealing material 37, and the second sealing material 39, and the end of the hydrogen separation cylinder 3 is inserted into the mounting fitting 5. Fit into the recess 33.
Next, the fixing bracket 11 is fitted from the distal end side of the hydrogen separation cylinder 3, the screw portion 43 of the fixing bracket 11 and the screw portion 23 of the mounting bracket 5 are screwed together, and the pressing bracket 9 is connected to the proximal end side by the fixing bracket 11. Tighten to.

その後、水素分離筒３の先端側より保護スリーブ１３を被せ、保護スリーブ１３の複数箇所をＮｉ線やＰｔ線等の金属ワイヤ４７で縛って、保護スリーブ１３の先端側を閉塞するとともに、保護スリーブ１３を水素分離筒３に固定し、水素分離装置１を完成する。   Thereafter, the protective sleeve 13 is put on the front end side of the hydrogen separation cylinder 3, and a plurality of portions of the protective sleeve 13 are bound with metal wires 47 such as Ni wire and Pt wire to close the front end side of the protective sleeve 13, and the protective sleeve 13 is fixed to the hydrogen separator cylinder 3 to complete the hydrogen separator 1.

ｄ）この様に、本実施形態では、図４に拡大して示す様に、水素分離筒３の表面を糸で編んだ保護スリーブ１３で覆うので、十分な通気性を確保できるとともに、外周壁５５等の表面から脱落した金属微粒子等の異物６７が、水素分離筒３の表面（即ち水素透過膜２１）に付着することを防止できる。そのため、水素透過膜２１に孔があいたり、水素透過膜２１の性能が低下することを防止できる。   d) Thus, in this embodiment, as shown in an enlarged view in FIG. 4, the surface of the hydrogen separation cylinder 3 is covered with the protective sleeve 13 knitted with yarn, so that sufficient air permeability can be secured and the outer peripheral wall It is possible to prevent foreign matter 67 such as metal fine particles that have fallen off from the surface 55 or the like from adhering to the surface of the hydrogen separation cylinder 3 (that is, the hydrogen permeable membrane 21). Therefore, it is possible to prevent a hole from being formed in the hydrogen permeable membrane 21 and a decrease in the performance of the hydrogen permeable membrane 21.

つまり、前記保護スリーブ１３は、異物６７の侵入を防止できる程度に細かいが、ガスの透過には十分に大きな間隙を有している編み物により構成されているので、異物６７の侵入を防止できるとともに、水素分離筒３にて分離された水素を保護スリーブ１３を介して反応管５３内に十分に供給することができる。   That is, the protective sleeve 13 is fine enough to prevent the entry of the foreign matter 67, but is formed of a knitted fabric having a sufficiently large gap for the permeation of gas. The hydrogen separated in the hydrogen separation cylinder 3 can be sufficiently supplied into the reaction tube 53 via the protective sleeve 13.

しかも、水素分離筒３にて分離された水素は、保護スリーブ１３を介して外周側に供給される構成であるので、この（外部に向かって流出する）水素ガス自体が異物６７の接近を妨害するという利点もある。   Moreover, since the hydrogen separated in the hydrogen separation cylinder 3 is supplied to the outer peripheral side via the protective sleeve 13, the hydrogen gas itself (flowing outward) obstructs the approach of the foreign matter 67. There is also an advantage of doing.

また、本実施形態では、保護スリーブ１３は、アルミナ等の繊維を編み上げた部材であるので、従来の様な高温での熱処理が不要であり、水素透過膜２１に悪影響を与えることがなく、水素分離筒３の外側に嵌め込むだけで、容易に取り付けが可能である。
しかも、この保護スリーブ１３は、硬質のセラミック焼結体ではなく、水素分離筒３よりはるかに柔軟な部材であるので、水素透過膜２１を破損し難いという利点がある。 In this embodiment, since the protective sleeve 13 is a member made of braided fibers such as alumina, heat treatment at a high temperature as in the conventional case is unnecessary, and the hydrogen permeable membrane 21 is not adversely affected. It can be easily attached by simply fitting it to the outside of the separation cylinder 3.
Moreover, since the protective sleeve 13 is not a hard ceramic sintered body but a member that is much more flexible than the hydrogen separation cylinder 3, there is an advantage that the hydrogen permeable membrane 21 is hardly damaged.

なお、本実施形態の水素分離装置１は、水素分離筒３の一端側（開放端）のみを固定した片持ち式であるが、水素分離筒３の振動等に対する安定性を増すために、水素分離筒３の閉塞端側を反応管５３等に固定しても良い。   The hydrogen separation apparatus 1 of the present embodiment is a cantilever type in which only one end side (open end) of the hydrogen separation cylinder 3 is fixed. However, in order to increase the stability against vibrations of the hydrogen separation cylinder 3, The closed end side of the separation cylinder 3 may be fixed to the reaction tube 53 or the like.

また、本実施形態は、水素分離筒３の内部に原料ガスを供給し、水素分離筒３により水素が分離され、その外周側より保護スリーブ１３を介して反応管５３内に水素が供給される形態であるが、反応管５３内に原料ガスを供給し、保護スリーブ１３により原料ガスが透過して、水素分離筒３により水素が分離され、水素分離筒３の内部に水素が供給され、内挿管５０、配管６１を介して水素を取り出すといった形態でも、何ら問題はない。
［第２実施形態］
次に、第２実施形態について説明するが、前記第１実施形態と同様な内容の説明は省略する。 In the present embodiment, the source gas is supplied into the hydrogen separation cylinder 3, hydrogen is separated by the hydrogen separation cylinder 3, and hydrogen is supplied into the reaction tube 53 from the outer peripheral side via the protective sleeve 13. Although it is a form, raw material gas is supplied in the reaction tube 53, raw material gas permeate | transmits by the protective sleeve 13, hydrogen is isolate | separated by the hydrogen separation cylinder 3, hydrogen is supplied inside the hydrogen separation cylinder 3, There is no problem even in the form of taking out hydrogen through the intubation 50 and the piping 61.
[Second Embodiment]
Next, the second embodiment will be described, but the description of the same content as the first embodiment will be omitted.

図５に示す様に、本実施形態の水素分離装置７１では、両端が開放された円筒状の水素分離筒７３が使用されており、この水素分離筒７３の軸方向の両側に、前記第１実施形態と同様に、取付金具７５、７７、シール部材７９、８１、押圧金具８３、８５、固定金具８７、８９からなる固定構造が形成されている。   As shown in FIG. 5, in the hydrogen separation device 71 of the present embodiment, a cylindrical hydrogen separation cylinder 73 that is open at both ends is used. Similar to the embodiment, a fixing structure including mounting brackets 75 and 77, seal members 79 and 81, pressing brackets 83 and 85, and fixing brackets 87 and 89 is formed.

つまり、水素分離筒７３の軸方向には、同図の左右対称に、取付金具７５、シール部材７９、押圧金具８３、固定金具８７からなる一方の固定構造と、取付金具７７、シール部材８１、押圧金具８５、固定金具８９からなる他方の固定構造とが設けられている。   That is, in the axial direction of the hydrogen separation cylinder 73, one fixing structure including the mounting bracket 75, the seal member 79, the pressing bracket 83, and the fixing bracket 87, the mounting bracket 77, the seal member 81, The other fixing structure including the pressing metal 85 and the fixing metal 89 is provided.

特に本実施形態では、水素分離筒７３の外周、詳しくは、左右の固定金具８７、８９の間の水素分離筒７３には、前記第１実施形態と同様な保護スリーブ９１（但し両端は開放された筒状部材）が外嵌され、水素分離筒７３の外側表面を隙間無く覆っている。   In particular, in the present embodiment, the outer periphery of the hydrogen separation cylinder 73, specifically, the hydrogen separation cylinder 73 between the left and right fixing brackets 87 and 89, is provided with a protective sleeve 91 similar to that of the first embodiment (however, both ends are opened). (A cylindrical member) is externally fitted and covers the outer surface of the hydrogen separation cylinder 73 without a gap.

そして、本実施形態では、例えば同図の右側から原料ガスを供給し、その反応後の原料ガスは同図の左側から排出される。また、水素分離筒７３で分離された水素は、水素分離筒７３の外周側から、保護スリーブ９１を介して反応管９３内に供給される。   And in this embodiment, source gas is supplied from the right side of the figure, for example, and the source gas after the reaction is discharged | emitted from the left side of the figure. Further, the hydrogen separated by the hydrogen separation cylinder 73 is supplied from the outer peripheral side of the hydrogen separation cylinder 73 into the reaction tube 93 through the protective sleeve 91.

本実施形態においても、前記第１実施形態と同様の効果を奏する。また、水素分離筒７３の両端が固定されているので、安定性が高いという利点がある。
なお、この変形例として、両端が開放された円筒状の水素分離筒を用いるが、水素分離装置の軸方向の一方は閉塞されている構成も採用できる。 Also in this embodiment, there exists an effect similar to the said 1st Embodiment. Moreover, since both ends of the hydrogen separation cylinder 73 are fixed, there is an advantage that the stability is high.
As this modification, a cylindrical hydrogen separation cylinder having both ends opened is used, but a configuration in which one of the hydrogen separation devices in the axial direction is closed can also be adopted.

次に、実際に上述した水素分離装置を備えた水素製造装置を作製して、その性能を確認した実験について説明する。
実験に使用する試料として、前記第１実施形態と同様な水素製造装置を作製した。 Next, an experiment in which a hydrogen production apparatus equipped with the above-described hydrogen separation apparatus was actually manufactured and its performance was confirmed will be described.
As a sample used for the experiment, a hydrogen production apparatus similar to that of the first embodiment was produced.

そして、この水素製造装置を用い、６００℃で、水素分離筒内に水素を導入し、１次側原料ガスとして水素を０．１ＭＰａＧで供給し、２次側０ＭＰａＧで、１００時間連続して水素を透過した。   Then, using this hydrogen production apparatus, hydrogen is introduced into the hydrogen separation cylinder at 600 ° C., hydrogen is supplied at 0.1 MPaG as the primary side source gas, and hydrogen is continuously supplied at 0 MPaG on the secondary side for 100 hours. Penetrated.

その後、水素製造装置から水素分離装置を取り出し、水素分離筒におけるガスのリークの有無を調べた。具体的には、水素分離筒を水中に入れ、水素分離装置の取付金具側から、Ｈｅガスを０．８ＭＰａＧで供給し、リーク箇所を確認した。   Thereafter, the hydrogen separator was taken out from the hydrogen production apparatus, and the presence or absence of gas leakage in the hydrogen separator was examined. Specifically, the hydrogen separation cylinder was put in water, He gas was supplied at 0.8 MPaG from the mounting bracket side of the hydrogen separation apparatus, and the leak location was confirmed.

次に、そのリーク箇所を切り出し、ＳＥＭ（走査型電子顕微鏡）にて、リーク箇所の状態を調べた。
その結果、本実施例では、リーク箇所において、金属異物の付着に起因する欠陥は見つからなかった。 Next, the leaked portion was cut out, and the state of the leaked portion was examined with an SEM (scanning electron microscope).
As a result, in this example, no defect due to the adhesion of the metal foreign matter was found at the leak location.

尚、本発明は前記実施形態になんら限定されるものではなく、本発明を逸脱しない範囲において種々の態様で実施しうることはいうまでもない。   In addition, this invention is not limited to the said embodiment at all, and it cannot be overemphasized that it can implement with a various aspect in the range which does not deviate from this invention.

第１実施形態の水素分離装置を軸方向に沿って破断して示す断面図である。It is sectional drawing which fractures | ruptures and shows the hydrogen separator of 1st Embodiment along an axial direction. 第１実施形態の水素分離装置を示す正面図である。It is a front view which shows the hydrogen separator of 1st Embodiment. 第１実施形態の水素製造装置を示し、（ａ）は（ｂ）のＡ−Ａ’断面図、（ｂ）は反応管を軸方向に破断して示す水素製造装置の正面図である。The hydrogen production apparatus of 1st Embodiment is shown, (a) is A-A 'sectional drawing of (b), (b) is a front view of the hydrogen production apparatus which fractures | ruptures and shows a reaction tube to an axial direction. 第１実施形態の水素分離装置における保護スリーブに機能を説明する説明図である。It is explanatory drawing explaining a function to the protection sleeve in the hydrogen separator of 1st Embodiment. 第２実施形態の水素分離装置を軸方向に沿って破断して示す断面図である。It is sectional drawing which fractures | ruptures and shows the hydrogen separator of 2nd Embodiment along an axial direction.

符号の説明Explanation of symbols

１、７１…水素分離装置
３、７３…水素分離筒
５、７５、７７…取付金具
１３、９１…保護スリーブ
２１…水素透過膜
４７…金属ワイヤ
５３、９３…反応管（収納容器） DESCRIPTION OF SYMBOLS 1,71 ... Hydrogen separator 3, 73 ... Hydrogen separation cylinder 5, 75, 77 ... Mounting bracket 13, 91 ... Protection sleeve 21 ... Hydrogen permeable membrane 47 ... Metal wire 53, 93 ... Reaction tube (storage container)

Claims (3)

金属製の反応管内に収容される水素分離筒であって、原料ガスから水素を選択して分離する水素透過膜が外側に形成された水素分離筒を備えた水素分離装置において、
前記水素透過膜の外側の表面を覆うように、前記反応管からの微粒子が前記水素透過膜に到ることを防止する保護部材を配置するとともに、
前記保護部材は、セラミックの繊維からなる糸を編み上げた筒状体であって、水素ガスの透過量が、８０％以上であることを特徴とする水素分離装置。 In a hydrogen separation apparatus including a hydrogen separation cylinder housed in a metal reaction tube and having a hydrogen permeable membrane formed on the outside for selecting and separating hydrogen from a source gas,
A protective member for preventing fine particles from the reaction tube from reaching the hydrogen permeable membrane is disposed so as to cover the outer surface of the hydrogen permeable membrane,
The protective member is a cylindrical body having braided yarn consisting of fibers of ceramic, permeation amount of hydrogen gas, the hydrogen separation apparatus, characterized in that less than 80%. 前記保護部材を形成する繊維の直径が、０．５〜１００μｍであることを特徴とする請求項１に記載の水素分離装置。   2. The hydrogen separator according to claim 1, wherein a diameter of a fiber forming the protective member is 0.5 to 100 μm. 金属製の反応管内に収容される水素分離筒であって、原料ガスから水素を選択して分離する水素透過膜が外側に形成された水素分離筒を備えた水素分離装置において、
前記水素透過膜の外側の表面を覆うように、前記反応管からの微粒子が前記水素透過膜に到ることを防止する保護部材を配置するとともに、
前記保護部材は、セラミックの繊維からなる糸を編み上げた筒状体であって、通気性を有するとともに、０．５μｍ以上の微粒子が透過できない構造を有することを特徴とする水素分離装置。 In a hydrogen separation apparatus including a hydrogen separation cylinder housed in a metal reaction tube and having a hydrogen permeable membrane formed on the outside for selecting and separating hydrogen from a source gas,
A protective member for preventing fine particles from the reaction tube from reaching the hydrogen permeable membrane is disposed so as to cover the outer surface of the hydrogen permeable membrane,
The hydrogen separator according to claim 1, wherein the protective member is a cylindrical body formed by knitting a thread made of ceramic fibers, has air permeability, and has a structure in which fine particles of 0.5 μm or more cannot permeate.
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