JPH07112111A - Gaseous hydrogen separator - Google Patents
Gaseous hydrogen separatorInfo
- Publication number
- JPH07112111A JPH07112111A JP5259603A JP25960393A JPH07112111A JP H07112111 A JPH07112111 A JP H07112111A JP 5259603 A JP5259603 A JP 5259603A JP 25960393 A JP25960393 A JP 25960393A JP H07112111 A JPH07112111 A JP H07112111A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen gas
- flange
- gas separation
- tube
- ceramics
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052739 hydrogen Inorganic materials 0.000 title abstract description 6
- 239000001257 hydrogen Substances 0.000 title abstract description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 title abstract 5
- 239000000919 ceramic Substances 0.000 claims abstract description 74
- 238000000926 separation method Methods 0.000 claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
- 239000007789 gas Substances 0.000 claims abstract description 32
- 239000000853 adhesive Substances 0.000 claims abstract description 10
- 230000001070 adhesive effect Effects 0.000 claims abstract description 10
- 238000005304 joining Methods 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 72
- 239000012528 membrane Substances 0.000 claims description 13
- 239000012466 permeate Substances 0.000 claims description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 12
- 238000000576 coating method Methods 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 6
- 229910052763 palladium Inorganic materials 0.000 abstract description 6
- 238000007747 plating Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 description 14
- 230000002093 peripheral effect Effects 0.000 description 7
- 229910001252 Pd alloy Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005219 brazing Methods 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 239000007767 bonding agent Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 229910000833 kovar Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/0271—Perovskites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0405—Purification by membrane separation
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Combustion & Propulsion (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、水素ガスを含有する被
処理ガスから水素ガス成分を選択的かつ効率的に分離す
るための水素ガス分離装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrogen gas separation device for selectively and efficiently separating a hydrogen gas component from a gas to be treated containing hydrogen gas.
【０００２】[0002]
【従来の技術】水素ガスは石油化学の基本素材ガスとし
て大量に使用され、又クリーンなエネルギー源として大
きな期待が寄せられている。高純度な水素ガスは、天然
ガス、ナフサ等を原料として各種の処理手段により処理
して製造された水素含有ガスから水素ガスを分離するこ
とにより得られる。2. Description of the Related Art Hydrogen gas is used in large quantities as a basic material gas for petrochemicals, and is expected to be a clean energy source. High-purity hydrogen gas can be obtained by separating hydrogen gas from a hydrogen-containing gas produced by processing natural gas, naphtha, or the like by various processing means.
【０００３】水素ガスを分離する有効な方法として、水
素ガス分離膜を用いた方法が知られており、例えば特開
昭６２−２７３０３０号公報、特開昭６３−１７１６１
７号公報には、多孔質ガラス、多孔質セラミックス、又
は多孔質酸化アルミニウム等の無機多孔質支持体の一表
面側に、水素ガスを選択的に透過させる選択透過能を有
するパラジウム又はパラジウム合金を被着した透過膜が
開示されている。As an effective method for separating hydrogen gas, a method using a hydrogen gas separation membrane is known, for example, Japanese Patent Laid-Open Nos. 62-273030 and 63-17161.
No. 7 discloses a palladium or palladium alloy having a selective permeation capacity for selectively permeating hydrogen gas on one surface side of an inorganic porous support such as porous glass, porous ceramics, or porous aluminum oxide. A deposited permeable membrane is disclosed.
【０００４】[0004]
【発明が解決しようとする課題】水素ガス分離装置は、
ガス分離体の一方の側より、水素ガスを含有する被処理
ガスを導入し、水素ガスのみがガス分離体を透過し、ガ
ス分離体の他方の側より、精製された水素ガスが得られ
る構造を有する。したがって、被処理ガス側と精製ガス
側とを気密に分離する必要があり、ガス分離体と支持体
との接合部から、被処理ガスが精製ガス側に漏洩しない
ことが必要となる。DISCLOSURE OF INVENTION Problems to be Solved by the Invention
A structure in which a gas to be treated containing hydrogen gas is introduced from one side of the gas separator, only hydrogen gas permeates the gas separator, and purified hydrogen gas is obtained from the other side of the gas separator. Have. Therefore, it is necessary to hermetically separate the target gas side and the purified gas side, and it is necessary that the target gas does not leak to the purified gas side from the joint between the gas separator and the support.
【０００５】一方、このような水素ガス分離膜を使用し
て水素ガスを効率良く分離するには、ガス分離膜中で水
素ガスが拡散する速度を早くするため、５〜１０気圧で
３００℃以上、好ましくは５００℃以上という高温、高
圧で処理することが有利である。このような高温、高圧
下で水素ガス分離処理を行なうに当っては、水素ガス分
離膜を高圧容器内において如何に支持するかが問題とな
る。即ち、高温、高圧の条件下においても水素ガス分離
膜の支持部が耐久性を有することは勿論のこと、当該支
持部から被処理ガス、分離された水素ガスなどが漏洩し
ないこと、さらにできるだけ大量にしかも効率的に水素
ガスを分離するために、高圧容器内に多くの水素ガス分
離膜を収納することが要請される。On the other hand, in order to efficiently separate hydrogen gas using such a hydrogen gas separation membrane, in order to accelerate the diffusion rate of hydrogen gas in the gas separation membrane, the temperature is 5 to 10 atmospheres and 300 ° C. or more. It is advantageous to perform the treatment at a high temperature, preferably 500 ° C. or higher, and a high pressure. In carrying out the hydrogen gas separation treatment under such a high temperature and high pressure, how to support the hydrogen gas separation membrane in the high pressure container becomes a problem. That is, the support portion of the hydrogen gas separation membrane is not only durable even under high temperature and high pressure conditions, the gas to be treated, the separated hydrogen gas, etc. do not leak from the support portion, and a large amount is possible. Moreover, in order to efficiently separate the hydrogen gas, it is required to store many hydrogen gas separation membranes in the high-pressure container.
【０００６】しかしながら、上記したような水素ガス分
離膜の支持部を有する水素ガス分離装置は知られていな
い。したがって、本発明は水素ガス分離膜の支持具合に
工夫をした新規な水素ガス分離装置を提供することを目
的とするものである。However, a hydrogen gas separation device having the above-mentioned hydrogen gas separation membrane supporting portion is not known. Therefore, an object of the present invention is to provide a novel hydrogen gas separation device in which the support condition of the hydrogen gas separation membrane is devised.
【０００７】[0007]
【課題を解決するための手段】すなわち、本発明によれ
ば、多孔質セラミックス管の少なくとも一側に、水素ガ
スを選択的に透過させる選択透過能を有する金属膜を備
えた水素ガス分離管を、該水素ガス分離管の一端を、ガ
スを透過しない緻密質セラミックス製フランジに貫通さ
せ該フランジに接着固定した状態で支持して構成される
水素ガス分離装置であって、多孔質セラミックス管と緻
密質セラミックス製フランジとを接合した後に、該接合
部表面と該多孔質セラミックス管の少なくとも一側に前
記金属膜を被覆処理してなることを特徴とする水素ガス
分離装置、が提供される。That is, according to the present invention, there is provided a hydrogen gas separation tube provided with a metal membrane having a selective permeation capacity for selectively permeating hydrogen gas on at least one side of a porous ceramics tube. A hydrogen gas separation device configured to support one end of the hydrogen gas separation pipe through a dense ceramics flange that does not allow gas to pass through and to be adhered and fixed to the flange. There is provided a hydrogen gas separation device, characterized in that the surface of the joint portion and at least one side of the porous ceramics tube are coated with the metal film after the flanges made of fine ceramics are joined.
【０００８】また、本発明によれば、多孔質セラミック
ス管の少なくとも一側に、水素ガスを選択的に透過させ
る選択透過能を有する金属膜を備えた水素ガス分離管
を、該水素ガス分離管の一端を、ガスを透過しない緻密
質セラミックス製フランジに貫通させて接着固定し、更
に該緻密質セラミックス製フランジの外周部を金属製フ
ランジに接合して構成される水素ガス分離装置であっ
て、多孔質セラミックス管と緻密質セラミックス製フラ
ンジとを接合した後に、該接合部表面と該多孔質セラミ
ックス管の少なくとも一側に前記金属膜を被覆処理して
なることを特徴とする水素ガス分離装置、が提供され
る。なお、本発明において、多孔質セラミックス管と緻
密質セラミックス製フランジとの接合には、耐熱性の無
機質接着剤を用いるのが好ましい。Further, according to the present invention, a hydrogen gas separation pipe having a metal membrane having a selective permeation ability for selectively permeating hydrogen gas is provided on at least one side of the porous ceramic pipe. A hydrogen gas separation device configured by piercing a dense ceramics flange that does not allow gas to pass therethrough and adhering and fixing it, and further bonding an outer peripheral portion of the dense ceramics flange to a metal flange, After joining the porous ceramics pipe and the dense ceramics flange, at least one side of the joining portion surface and the porous ceramics pipe is coated with the metal film, which is characterized in that the hydrogen gas separation device, Will be provided. In the present invention, it is preferable to use a heat resistant inorganic adhesive for joining the porous ceramic tube and the dense ceramic flange.
【０００９】[0009]
【作用】本発明の水素ガス分離装置においては、水素ガ
ス分離管をフランジに貫通し、接着固定して支持する構
造に特徴がある。本発明者は、金属膜を被覆した多孔質
セラミックス管を、フランジに貫通させ接着固定し支持
する構造に関し、種々の角度から検討した。The hydrogen gas separation apparatus of the present invention is characterized by a structure in which the hydrogen gas separation pipe is penetrated through the flange and is fixedly bonded and supported. The present inventor has studied from various angles regarding a structure in which a porous ceramics tube coated with a metal film is penetrated through a flange so as to be adhesively fixed.
【００１０】まず、パラジウム又はパラジウム合金等の
金属膜を、例えば化学メッキ法によりその外表面に被覆
した多孔質セラミックス管を作製し、次いでこの多孔質
セラミックス管の外径より僅かに大きい直径の貫通孔を
備えた緻密質セラミックスからなるフランジを用意し、
フランジの貫通孔に貫通させた状態で接着固定し支持し
ようとした。この場合、金属とセラミックスとの接合と
なるが、接着剤としてセメントなどの無機質接着剤を用
いると、無機質接着剤で形成された接合部は緻密になら
ないため、この接合部からガス漏れが生じるという不具
合があった。First, a porous ceramic tube is prepared by coating a metal film of palladium or a palladium alloy on the outer surface thereof by, for example, a chemical plating method, and then a porous ceramic tube having a diameter slightly larger than the outer diameter of the porous ceramic tube is formed. Prepare a flange made of dense ceramics with holes,
An attempt was made to adhesively fix and support the through hole of the flange. In this case, the metal and ceramics will be joined, but if an inorganic adhesive such as cement is used as the adhesive, the joint formed by the inorganic adhesive will not be dense, and gas leakage will occur from this joint. There was a problem.
【００１１】一方、金属製のフランジを用い、これと金
属膜を被覆した多孔質セラミックス管をロウ材を用いて
接合する場合には、フランジの貫通孔内径と多孔質セラ
ミックス管外径との隙間を１００μｍ以下に管理しない
とロウ付けが適切に行なわれないが、多孔質セラミック
ス管外径の管理が実際上極めて困難である。そこで、本
発明者は種々検討を重ね、多孔質セラミックス管を緻密
質セラミックスからなるフランジに貫通し接合した後、
多孔質セラミックス管と当該接合部の表面に金属膜を被
覆処理することにより、前記した不具合を解消すること
ができることを見い出したのである。On the other hand, when a metal flange is used and the porous ceramic tube coated with a metal film is joined with a brazing material, a gap between the inner diameter of the through hole of the flange and the outer diameter of the porous ceramic tube is used. The brazing cannot be properly performed unless the diameter is controlled to 100 μm or less, but it is actually extremely difficult to control the outer diameter of the porous ceramic tube. Therefore, the present inventor has made various studies, and after the porous ceramic tube is penetrated and joined to the flange made of the dense ceramic,
It has been found that the above-mentioned inconvenience can be eliminated by coating the surface of the porous ceramics tube and the joint portion with a metal film.
【００１２】また、本発明の水素ガス分離装置におい
て、多孔質セラミックス管の一端を緻密質セラミックス
製フランジに貫通させて接着固定した後に、多孔質セラ
ミックス管と当該接合部の表面に金属膜を被覆処理し、
さらに緻密質セラミックス製フランジの外周部を金属製
フランジに接合して構成すると、高温、高圧における耐
久性に優れるとともに、容器内に多数の水素ガス分離管
を工程上容易に収納できることから極めて好ましい。こ
こで、緻密質セラミックス製フランジの外周部と金属製
フランジの接合は、ロウ付けにより処理することが耐久
性、ガスの漏洩防止の観点から適切である。そして、こ
の場合のロウ付け処理は、金属製フランジの貫通孔内径
と緻密質セラミックス製フランジの外周部との隙間は所
定以上に緻密に制御、管理ができるので好ましい。Further, in the hydrogen gas separation apparatus of the present invention, one end of the porous ceramics pipe is penetrated through the dense ceramics flange and fixed by adhesion, and then the surface of the porous ceramics pipe and the joint portion is coated with a metal film. Process and
Further, it is extremely preferable to join the outer peripheral portion of the dense ceramic flange to the metal flange so as to have excellent durability at high temperature and high pressure and to easily store a large number of hydrogen gas separation tubes in the container in the process. Here, it is appropriate that the outer peripheral portion of the dense ceramic flange and the metal flange are joined by brazing from the viewpoint of durability and gas leakage prevention. The brazing process in this case is preferable because the gap between the inner diameter of the through hole of the metal flange and the outer peripheral portion of the dense ceramic flange can be controlled and managed more precisely than a predetermined level.
【００１３】本発明において、金属膜を被覆処理する方
法としては従来公知の方法が使用でき、例えば、化学メ
ッキ法、真空蒸着法、スパッタリング法等を用いること
ができる。また、多孔質セラミックス管と、緻密質セラ
ミックス製フランジとの接合に用いる接合剤としては、
耐熱性を有する無機質接着剤で、熱膨張が多孔質セラミ
ックス管と同等のモルタル、セメント、転移点が５００
℃以上のガラスなどが好ましく使用される。接合剤とし
てガラス等を用いた場合において、接合剤表面が滑らか
なときには、金属膜の剥離が生じる。この場合には、サ
ンドブラスト、エッチング等により、表面粗さをＲａ＝
０．０５〜１μｍに制御することで、剥離を防ぐことが
可能である。In the present invention, a conventionally known method can be used as a method for coating the metal film, for example, a chemical plating method, a vacuum vapor deposition method, a sputtering method or the like can be used. Further, as the bonding agent used for bonding the porous ceramics pipe and the dense ceramics flange,
A heat-resistant inorganic adhesive with a thermal expansion equivalent to that of a porous ceramics tube, mortar, cement and transition point of 500.
Glass or the like having a temperature of ℃ or higher is preferably used. When glass or the like is used as the bonding agent, peeling of the metal film occurs when the surface of the bonding agent is smooth. In this case, the surface roughness is Ra =
The peeling can be prevented by controlling the thickness to 0.05 to 1 μm.
【００１４】多孔質セラミックス管は、アルミナ、シリ
カ−アルミナ、ムライト、コージェライト、ジルコニア
等の材質からなるもので、例えば、セラミック質の粉末
材料を混練してパイプ状に押出成形後、焼成して製造さ
れる。緻密質セラミックス製フランジの被覆処理部分
は、必要に応じて表面粗さを制御することが好ましい。
これは、緻密質セラミックス製フランジの表面が鏡面で
ある場合には、接合後に行う金属膜の被覆処理におい
て、金属膜の剥離が生じることがあるためである。表面
粗さはＲａ＝０．０５〜１μｍに制御することが好まし
い。また、無機接着剤がガラスである場合も同様の制御
を行うことが好ましい。また、緻密質セラミックス製フ
ランジは、前記多孔質セラミックス管と同材質であるこ
とが好ましい。なお、緻密質セラミックス製フランジの
外周部に接合する金属製フランジとしては、ＳＵＳ、イ
ンコネル、コバール等が使用できる。The porous ceramic tube is made of a material such as alumina, silica-alumina, mullite, cordierite, or zirconia. For example, a ceramic powder material is kneaded, extruded into a pipe shape, and then fired. Manufactured. It is preferable to control the surface roughness of the coated portion of the dense ceramic flange as necessary.
This is because when the surface of the dense ceramics flange is a mirror surface, the metal film may be peeled off in the coating process of the metal film performed after the joining. The surface roughness is preferably controlled to Ra = 0.05 to 1 μm. Further, it is preferable to perform the same control even when the inorganic adhesive is glass. Further, the dense ceramic flange is preferably made of the same material as the porous ceramic tube. It should be noted that SUS, Inconel, Kovar, or the like can be used as the metal flange joined to the outer peripheral portion of the dense ceramic flange.
【００１５】[0015]
【実施例】以下、本発明を図示の実施例に基づき更に詳
しく説明するが、本発明はこれらの実施例に限られるも
のではない。EXAMPLES The present invention will now be described in more detail based on the illustrated examples, but the present invention is not limited to these examples.
【００１６】図１は本発明の水素ガス分離装置を示す断
面図、図２は図１の一部拡大断面図で、図１に示す高圧
容器１０内に筒状で複数本の水素ガス分離管１１を収納
して形成されている。フランジ１２は、水素ガス分離管
１１の外径より僅かに大きい直径の貫通孔１２ａを複数
備え、またフランジ１３は、貫通孔１２ａと同じ大きさ
の直径で貫通していない孔１３ａを複数備えており、水
素ガス分離管１１はその一端をフランジ１２の貫通孔１
２ａに貫通させ開口した状態で支持されるとともに、他
端はフランジ１３の孔１３ａに挿入されて目封じされて
いる。FIG. 1 is a sectional view showing a hydrogen gas separation apparatus of the present invention, and FIG. 2 is a partially enlarged sectional view of FIG. 1, showing a plurality of cylindrical hydrogen gas separation tubes in a high-pressure container 10 shown in FIG. It is formed by housing 11. The flange 12 has a plurality of through holes 12a having a diameter slightly larger than the outer diameter of the hydrogen gas separation pipe 11, and the flange 13 has a plurality of holes 13a having the same size as the through holes 12a and not passing through. The hydrogen gas separation pipe 11 has one end at the through hole 1 of the flange 12.
It is supported by being penetrated through 2a and opened, and the other end is inserted into a hole 13a of the flange 13 and sealed.
【００１７】ここで、本実施例に示す水素ガス分離装置
では、図３に示すように、水素ガス分離管１１は、多孔
質セラミックス管１４をフランジ１２の貫通孔１２ａ及
びフランジ１３の孔１３ａにそれぞれ貫通及び挿入させ
た状態でセメントなどの無機質接着剤にて接合した後
に、接合部１５と多孔質セラミックス管１４の一側表面
を覆ってパラジウム又はパラジウム合金等の金属膜２６
を化学メッキ法等で被覆処理して形成してある。そし
て、上部側のフランジ１２の外周部が、図２に示す支持
プレート１６、１７で支持されている。Here, in the hydrogen gas separation apparatus according to the present embodiment, as shown in FIG. 3, the hydrogen gas separation tube 11 has a porous ceramic tube 14 in the through hole 12a of the flange 12 and the hole 13a of the flange 13. After being bonded with an inorganic adhesive such as cement in a state of being penetrated and inserted, respectively, a metal film 26 of palladium or a palladium alloy, etc., covering the bonding portion 15 and the one side surface of the porous ceramics tube 14.
Is formed by coating with a chemical plating method or the like. The outer peripheral portion of the upper flange 12 is supported by the support plates 16 and 17 shown in FIG.
【００１８】なお、図１中の１８、１９は支持プレート
１７を保持するフランジであり、２０は被処理ガスの流
入路である第１パイプ、２１は処理済ガスの流出路であ
る第２パイプ、２２は分離された水素ガスの流出路であ
る第３パイプを示している。In FIG. 1, 18 and 19 are flanges for holding the support plate 17, 20 is a first pipe which is an inflow passage of the gas to be treated, and 21 is a second pipe which is an outflow passage of the treated gas. 22 indicates a third pipe which is an outflow passage of the separated hydrogen gas.
【００１９】以上の構成を有する水素ガス分離装置にお
いて、第１パイプ２０から被処理ガスが高圧容器１０内
に供給される。被処理ガスとしては、例えば水素ガスお
よび炭酸ガスを主成分とする５００℃〜６００℃の高温
で、５〜１０気圧程度の高圧のものである。被処理ガス
は、第２パイプ２１から流出するが、その間被処理ガス
中の水素ガス成分が水素ガス分離管１１を選択的に透過
して水素ガス分離管１１の内側に入る。水素ガス分離管
１１の内側に入った水素ガス成分は、第３パイプ２２か
ら流出する。In the hydrogen gas separation apparatus having the above structure, the gas to be treated is supplied from the first pipe 20 into the high pressure vessel 10. The gas to be processed is, for example, a gas containing hydrogen gas and carbon dioxide gas as main components at a high temperature of 500 ° C. to 600 ° C. and a high pressure of about 5 to 10 atm. The gas to be processed flows out from the second pipe 21, while the hydrogen gas component in the gas to be processed selectively permeates the hydrogen gas separation pipe 11 and enters the inside of the hydrogen gas separation pipe 11. The hydrogen gas component that has entered the hydrogen gas separation pipe 11 flows out from the third pipe 22.
【００２０】このように被処理ガスから水素ガス成分が
分離されるが、上記実施例においては、水素ガス分離管
１１は、図３に示すように多孔質セラミックス管１４を
フランジ１２、１３の貫通孔１２ａ，孔１３ａにそれぞ
れ貫通及び挿入させた状態でセメントなどの無機質接着
剤にて接合した後に、接合部１５と多孔質セラミックス
管１４を一側表面を覆ってパラジウム又はパラジウム合
金等の金属膜２６を化学メッキ法等で被覆処理して形成
してあるので、高温、高圧下で十分な耐久性を有し、し
かも接合部１５からのガス漏れを防止できる。As described above, the hydrogen gas component is separated from the gas to be treated. In the above embodiment, the hydrogen gas separation pipe 11 penetrates the porous ceramic pipe 14 through the flanges 12 and 13 as shown in FIG. After bonding with an inorganic adhesive such as cement in a state of penetrating and inserting into the holes 12a and 13a, respectively, the bonding portion 15 and the porous ceramics tube 14 are covered on one side surface with a metal film such as palladium or palladium alloy. Since 26 is formed by coating by a chemical plating method or the like, it has sufficient durability under high temperature and high pressure and can prevent gas leakage from the joint portion 15.
【００２１】また、図４に示すように、多孔質セラミッ
クス管１４の一端を緻密質セラミックス製フランジ２３
に貫通させて接着固定した後、多孔質セラミックス管１
４と当該接合部２４の一側表面を覆ってパラジウム又は
パラジウム合金等の金属膜２６を化学メッキ法等で被覆
処理し、次いで、さらに緻密質セラミックス製フランジ
２３の外周部を金属製フランジ２５に接合することによ
り、高温、高圧における耐久性に優れ、しかも高圧容器
内に多数の水素ガス分離管１１を工程上容易に収納する
ことができる水素ガス分離装置を製造することができ
る。Further, as shown in FIG. 4, one end of the porous ceramics pipe 14 is provided with a dense ceramics flange 23.
Porous ceramics tube 1
4 and one side surface of the joint portion 24 are covered with a metal film 26 of palladium or a palladium alloy by a chemical plating method or the like, and then the outer peripheral portion of the dense ceramic flange 23 is further formed into a metal flange 25. By joining, it is possible to manufacture a hydrogen gas separation device that has excellent durability at high temperature and high pressure and that can easily accommodate a large number of hydrogen gas separation pipes 11 in a high-pressure container in the process.
【００２２】[0022]
【発明の効果】以上説明したように、本発明によれば、
高温、高圧における耐久性に優れるほか、接合部でのガ
ス漏洩が防止され、しかも高圧容器内に多くの水素ガス
分離管を収納することができる水素ガス分離装置を提供
することができる。As described above, according to the present invention,
It is possible to provide a hydrogen gas separation device which has excellent durability at high temperature and high pressure, prevents gas leakage at the joint, and can accommodate many hydrogen gas separation pipes in a high pressure container.
【図１】本発明の水素ガス分離装置を示す断面図であ
る。FIG. 1 is a cross-sectional view showing a hydrogen gas separation device of the present invention.
【図２】図１の一部拡大断面図である。FIG. 2 is a partially enlarged cross-sectional view of FIG.
【図３】多孔質セラミックス管と緻密質セラミックス製
フランジとの接合部の拡大断面図である。FIG. 3 is an enlarged sectional view of a joint portion between a porous ceramics tube and a dense ceramics flange.
【図４】多孔質セラミックス管−緻密質セラミックス製
フランジ−金属製フランジの接合部の拡大断面図であ
る。FIG. 4 is an enlarged cross-sectional view of a joint portion of a porous ceramics tube, a dense ceramics flange, and a metal flange.
１０…高圧容器、１１…水素ガス分離管、１２，１３…
フランジ、１２ａ…貫通孔、１３ａ…孔、１４…多孔質
セラミックス管、１５…接合部、１６，１７…支持プレ
ート、１８，１９…フランジ、２０…第１パイプ、２１
…第２パイプ、２２…第３パイプ、２３…緻密質セラミ
ックス製フランジ、２４…接合部、２５…金属製フラン
ジ、２６…金属膜10 ... High-pressure container, 11 ... Hydrogen gas separation tube, 12, 13 ...
Flange, 12a ... Through hole, 13a ... Hole, 14 ... Porous ceramic tube, 15 ... Joint part, 16, 17 ... Support plate, 18, 19 ... Flange, 20 ... First pipe, 21
... second pipe, 22 ... third pipe, 23 ... dense ceramics flange, 24 ... joint, 25 ... metal flange, 26 ... metal film
Claims (3)
に、水素ガスを選択的に透過させる選択透過能を有する
金属膜を備えた水素ガス分離管を、該水素ガス分離管の
一端を、ガスを透過しない緻密質セラミックス製フラン
ジに貫通させ該フランジに接着固定した状態で支持して
構成される水素ガス分離装置であって、多孔質セラミッ
クス管と緻密質セラミックス製フランジとを接合した後
に、該接合部表面と該多孔質セラミックス管の少なくと
も一側に前記金属膜を被覆処理してなることを特徴とす
る水素ガス分離装置。1. A hydrogen gas separation tube provided with a metal membrane having a selective permeation capacity for selectively permeating hydrogen gas on at least one side of a porous ceramics tube, and one end of the hydrogen gas separation tube is provided with a gas. A hydrogen gas separation device configured to penetrate a dense ceramics flange that does not pass through and to be supported in a state of being adhered and fixed to the flange, wherein the porous ceramics tube and the dense ceramics flange are joined together, and thereafter the joining is performed. A hydrogen gas separation device, characterized in that at least one side of the surface of the porous ceramic tube and the porous ceramic tube are coated with the metal film.
に、水素ガスを選択的に透過させる選択透過能を有する
金属膜を備えた水素ガス分離管を、該水素ガス分離管の
一端を、ガスを透過しない緻密質セラミックス製フラン
ジに貫通させて接着固定し、更に該緻密質セラミックス
製フランジの外周部を金属製フランジに接合して構成さ
れる水素ガス分離装置であって、多孔質セラミックス管
と緻密質セラミックス製フランジとを接合した後に、該
接合部表面と該多孔質セラミックス管の少なくとも一側
に前記金属膜を被覆処理してなることを特徴とする水素
ガス分離装置。2. A hydrogen gas separation tube provided with a metal membrane having a selective permeation capacity for selectively permeating hydrogen gas on at least one side of a porous ceramics tube, and one end of the hydrogen gas separation tube is provided with a gas. A hydrogen gas separation device configured by piercing and adhering to a dense ceramics flange that does not permeate, and further bonding the outer periphery of the dense ceramics flange to a metal flange. A hydrogen gas separation device, characterized in that after the high quality ceramic flange is joined, the surface of the joint and at least one side of the porous ceramic tube are coated with the metal film.
クス製フランジとの接合に耐熱性の無機質接着剤を用い
る請求項１又は２に記載の水素ガス分離装置。3. The hydrogen gas separation device according to claim 1, wherein a heat-resistant inorganic adhesive is used for joining the porous ceramic tube and the dense ceramic flange.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25960393A JP3207635B2 (en) | 1993-10-18 | 1993-10-18 | Hydrogen gas separation device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25960393A JP3207635B2 (en) | 1993-10-18 | 1993-10-18 | Hydrogen gas separation device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07112111A true JPH07112111A (en) | 1995-05-02 |
| JP3207635B2 JP3207635B2 (en) | 2001-09-10 |
Family
ID=17336393
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25960393A Expired - Lifetime JP3207635B2 (en) | 1993-10-18 | 1993-10-18 | Hydrogen gas separation device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3207635B2 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0941759A1 (en) * | 1998-03-12 | 1999-09-15 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Method for producing an exchanger and exchanger |
| US6572837B1 (en) | 2000-07-19 | 2003-06-03 | Ballard Power Systems Inc. | Fuel processing system |
| JP2003533344A (en) * | 2000-05-19 | 2003-11-11 | イノセラミック ゲセルシャフト フュア イノベイティブ ケラミック エムベーハー | Separation module and manufacturing method thereof |
| JP2004019879A (en) * | 2002-06-19 | 2004-01-22 | Noritake Co Ltd | Seal unit, sealant and use thereof |
| JP2007014892A (en) * | 2005-07-08 | 2007-01-25 | Dainippon Printing Co Ltd | Hydrogen purification filter and production method of the same |
| US7255729B2 (en) | 2003-05-30 | 2007-08-14 | Noritake Co., Limited | Porous cylindrical-body module, structure for supporting porous cylindrical bodies, and method for fastening a supporting member |
| JP2007237146A (en) * | 2006-03-13 | 2007-09-20 | Ngk Insulators Ltd | Hydrogen gas separator fixing structure and hydrogen gas separation apparatus using it |
| JP2008246315A (en) * | 2007-03-29 | 2008-10-16 | Ngk Spark Plug Co Ltd | Hydrogen separation device and fuel cell |
| JP2014161782A (en) * | 2013-02-25 | 2014-09-08 | Meidensha Corp | Membrane unit and membrane unit complex |
| JP2014161781A (en) * | 2013-02-25 | 2014-09-08 | Meidensha Corp | Membrane module and membrane unit |
| WO2017106886A1 (en) * | 2015-12-21 | 2017-06-29 | Plansee Se | Membrane assembly with bonding layer |
-
1993
- 1993-10-18 JP JP25960393A patent/JP3207635B2/en not_active Expired - Lifetime
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0941759A1 (en) * | 1998-03-12 | 1999-09-15 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Method for producing an exchanger and exchanger |
| US6174490B1 (en) | 1998-03-12 | 2001-01-16 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek (Tno) | Method for producing an exchanger |
| JP2003533344A (en) * | 2000-05-19 | 2003-11-11 | イノセラミック ゲセルシャフト フュア イノベイティブ ケラミック エムベーハー | Separation module and manufacturing method thereof |
| US6572837B1 (en) | 2000-07-19 | 2003-06-03 | Ballard Power Systems Inc. | Fuel processing system |
| JP2004019879A (en) * | 2002-06-19 | 2004-01-22 | Noritake Co Ltd | Seal unit, sealant and use thereof |
| US7255729B2 (en) | 2003-05-30 | 2007-08-14 | Noritake Co., Limited | Porous cylindrical-body module, structure for supporting porous cylindrical bodies, and method for fastening a supporting member |
| JP2007014892A (en) * | 2005-07-08 | 2007-01-25 | Dainippon Printing Co Ltd | Hydrogen purification filter and production method of the same |
| JP2007237146A (en) * | 2006-03-13 | 2007-09-20 | Ngk Insulators Ltd | Hydrogen gas separator fixing structure and hydrogen gas separation apparatus using it |
| JP4490383B2 (en) * | 2006-03-13 | 2010-06-23 | 日本碍子株式会社 | Hydrogen gas separator fixing structure and hydrogen gas separator using the same |
| JP2008246315A (en) * | 2007-03-29 | 2008-10-16 | Ngk Spark Plug Co Ltd | Hydrogen separation device and fuel cell |
| JP2014161782A (en) * | 2013-02-25 | 2014-09-08 | Meidensha Corp | Membrane unit and membrane unit complex |
| JP2014161781A (en) * | 2013-02-25 | 2014-09-08 | Meidensha Corp | Membrane module and membrane unit |
| WO2017106886A1 (en) * | 2015-12-21 | 2017-06-29 | Plansee Se | Membrane assembly with bonding layer |
| US10751667B2 (en) | 2015-12-21 | 2020-08-25 | Plansee Se | Membrane assembly with a bonding layer |
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| Publication number | Publication date |
|---|---|
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