JP2960998B2 - Hydrogen gas separation membrane - Google Patents
Hydrogen gas separation membraneInfo
- Publication number
- JP2960998B2 JP2960998B2 JP3245430A JP24543091A JP2960998B2 JP 2960998 B2 JP2960998 B2 JP 2960998B2 JP 3245430 A JP3245430 A JP 3245430A JP 24543091 A JP24543091 A JP 24543091A JP 2960998 B2 JP2960998 B2 JP 2960998B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- separation membrane
- gas separation
- hydrogen
- porous support
- 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.)
- Expired - Lifetime
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Description
【０００１】[0001]
【産業上の利用分野】本発明は混合ガス中の水素ガスを
分離するための水素ガス分離膜に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrogen gas separation membrane for separating hydrogen gas in a mixed gas.
【０００２】[0002]
【従来の技術】省エネルギー型分離技術として、近年、
膜を用いた気体の分離法が注目されている。膜を用いる
水素を分離する方法はＰｄを含有する膜（Ｐｄ膜と略
す）又は特殊なガス分離膜により水素を含有する混合気
体から水素を分離する方法であり、従来次の如き方法が
採用されている。2. Description of the Related Art In recent years, as an energy-saving separation technology,
Attention has been paid to a gas separation method using a membrane. The method of separating hydrogen using a membrane is a method of separating hydrogen from a hydrogen-containing gas mixture using a Pd-containing membrane (abbreviated as a Pd membrane) or a special gas separation membrane, and the following method is conventionally employed. ing.
【０００３】（１）図１２に示すように、数μｍ〜数十
μｍの金属繊維を圧延焼結した金属多孔質支持体上にメ
ッキ法等の湿式法によりＰｄを含有する薄膜を形成させ
て水素ガス分離膜として使用する方法。(1) As shown in FIG. 12, a Pd-containing thin film is formed by a wet method such as a plating method on a metal porous support obtained by rolling and sintering a metal fiber of several μm to several tens μm. Method used as a hydrogen gas separation membrane.
【０００４】（２）又、上記の方法と比較し余り実用的
ではないが、ガラス、セラミックス等の無機質材料から
なる多孔質支持体にＰｄ膜を含有する薄膜を形成させて
水素ガス分離膜として使用する方法（特開昭６２−１２
１６１６号公報）。(2) Although not very practical compared with the above method, a thin film containing a Pd film is formed on a porous support made of an inorganic material such as glass or ceramics to form a hydrogen gas separation film. Method used (Japanese Unexamined Patent Publication No. Sho 62-12)
No. 1616).
【０００５】（３）更に、ガス分子の平均自由工程より
小さな細孔をもつ多孔質のガス分離膜による分離法、即
ちクヌーセン拡散法などもある。(3) There is also a separation method using a porous gas separation membrane having pores smaller than the mean free path of gas molecules, that is, a Knudsen diffusion method.
【０００６】[0006]
【発明が解決しようとする課題】（１）図１２に示すよ
うな金属多孔質支持体を使用する方法には次の問題があ
る。 支持体の細孔を均一な大きさで、かつ所望の開孔率
で形成せしめることが製造技術上難しく、通常、支持体
の細孔は大きいものから小さいものまで広範囲な細孔が
存在する。 この支持体上にメッキ法でＰｄ膜を成膜する際、Ｐ
ｄ金属の細孔内部への侵入、更に細孔を閉塞するには最
も大きな細孔に律則されるため、必然的にＰｄ膜が厚く
なる。 その結果、水素透過性能が低下し、高性能な水素ガ
ス分離膜が得られない。 図１２に示すように、その細孔は板厚方向に対し、
直線的でなく複雑な経路で形成されるため、圧損が大き
く水素の透過抵抗が大きくなる。(1) The method using a metal porous support as shown in FIG. 12 has the following problems. It is difficult in manufacturing technology to form the pores of the support with a uniform size and a desired porosity. Generally, the support has a wide range of pores from large to small. When a Pd film is formed on this support by plating,
The penetration of d metal into the pores and the closing of the pores are governed by the largest pores, so that the Pd film necessarily becomes thicker. As a result, the hydrogen permeation performance decreases, and a high-performance hydrogen gas separation membrane cannot be obtained. As shown in FIG. 12, the pores are in the thickness direction,
Since it is formed not in a straight line but in a complicated path, pressure loss is large and hydrogen permeation resistance is increased.
【０００７】（２）無機多孔質支持体にＰｄ膜を成膜さ
せる方法は上記問題の他に強度的に脆弱なため破損し易
く、更に他部材との接合（溶接など）が難しいという問
題がある。(2) In addition to the above-mentioned problems, the method of forming a Pd film on an inorganic porous support is fragile in terms of strength, so that it is easily broken, and it is difficult to join (welding, etc.) with other members. is there.
【０００８】（３）クヌーセン拡散による分離法は、一
般には分離膜として有機高分子膜が採用されるが、耐熱
性、耐薬品性等耐久性に劣るという不具合と高濃度の水
素ガスが得られ難いという問題がある。(3) In the separation method by Knudsen diffusion, an organic polymer membrane is generally employed as a separation membrane. However, such a method is inferior in durability such as heat resistance and chemical resistance, and high concentration hydrogen gas is obtained. There is a problem that it is difficult.
【０００９】本発明は上記技術水準に鑑み、従来技術に
おける上述の問題点を解決しうる高機能水素分離膜を提
供しようとするものである。The present invention has been made in view of the above-mentioned state of the art, and has as its object to provide a high-performance hydrogen separation membrane which can solve the above-mentioned problems in the prior art.
【００１０】[0010]
【課題を解決するための手段】本発明はレーザ法又はエ
ッチングにより孔あけ加工した金属多孔質支持体の表面
に、Ｐｄを含有する薄膜を重ね合わせ、前記金属多孔質
支持体とＰｄを含有する薄膜との間に薄層のバリア層を
介在させてなることを特徴とする水素ガス分離膜であ
る。 Means for Solving the Problems The present invention to the surface of the record over sitting or etched by drilling metal porous support, superposing the thin film containing Pd, the metal porous
A thin barrier layer between the support and the thin film containing Pd
Hydrogen gas separation membrane der characterized by comprising interposed therebetween
You.
【００１１】[0011]
【００１２】すなわち、本発明は金属多孔質支持体とし
て、従来の金属繊維・圧延焼結材にかわり、レーザ又は
エッチングにより穿孔し細孔を設けた支持体を使用する
こととし、Ｐｄ膜の成膜法をメッキ法等の湿式法ではな
く、圧延等の手段で薄くしたＰｄ膜を上記支持体に貼り
合わせて水素ガス分離膜として使用するようにし、更に
Ｐｄ膜と支持体との間に薄層のバリア層（セラミック、
金属酸化物）を介在させたものである。That is, according to the present invention, a metal porous support is used in place of the conventional metal fiber and rolled sintered material, and a support provided with holes by laser or etching to form a Pd film. rather than wet process plating method or the like film forming method, a thinned Pd film by a means such as rolling so as to use as a hydrogen gas separation membrane adhered to the support member, further
Between the Pd film and the support, a thin barrier layer (ceramic,
(Metal oxide).
【００１３】[0013]
【作用】（１）レーザ又はエッチングにて製造した金属
多孔質支持体は均一な大きさでしかも板厚方向にほぼ直
線的な細孔が形成される。また、孔径或いは開孔率も自
由に変えられ開孔率の大きな金属多孔質支持体が製造で
きる。(1) A metal porous support produced by laser or etching has pores of uniform size and substantially linear in the thickness direction. Further, the pore diameter or the porosity can be freely changed, and a metal porous support having a large porosity can be manufactured.
【００１４】（２）開孔率が大きくしかも板厚方向にほ
ぼ直線的な細孔が得られることから水素透過抵抗の小さ
な金属多孔質支持体を得ることができる。(2) A metal porous support having a small hydrogen permeation resistance can be obtained because pores are large and substantially linear pores are obtained in the thickness direction.
【００１５】（３）Ｐｄ膜の成膜法を従来のめっき法に
変わり貼り合わせ方式にしたことにより、めっき時に問
題となる細孔内部へのＰｄ金属の侵入防止が計れる。(3) By using a bonding method instead of a conventional plating method for forming a Pd film, it is possible to prevent the intrusion of Pd metal into the inside of the pores, which is a problem during plating.
【００１６】（４）更に、Ｐｄ膜と金属多孔質支持体と
の間に薄層のバリア層を介在させることにより、Ｐｄの
支持体金属への拡散が防止され、Ｐｄ膜の劣化を防止す
ることが可能となる。(4) Further, by interposing a thin barrier layer between the Pd film and the metal porous support, diffusion of Pd into the support metal is prevented, and deterioration of the Pd film is prevented. It becomes possible.
【００１７】[0017]
【実施例】（参考例１） 供試材として１８−８ステンレス鋼（ＪＩＳ規格：ＳＵ
Ｓ３０４）の薄板（７０ｍｍ×７０ｍｍ×１ｍｍ）を使
用し、この薄板の表面に微細なスポットに集光でき、金
属材料に対する反射率の小さなＹＡＧレーザを細孔径：
１０μｍ、細孔面積率が２０％となるように出力などを
調整、照射し金属多孔質支持体を製作し、細孔径の大き
さ、面積率（薄板の全表面積に対する貫通孔表面積の割
合）を調べた。EXAMPLES ( Reference Example 1) 18-8 stainless steel (JIS standard: SU
Using the thin plate (70 mm × 70 mm × 1 mm) of S304), a YAG laser capable of condensing a fine spot on the surface of this thin plate and having a small reflectance to a metal material is formed by using a YAG laser having a pore diameter of:
The output and the like are adjusted and irradiated so that the pore area ratio becomes 10% and the pore area ratio becomes 20%, and the metal porous support is manufactured, and the pore size and the area ratio (the ratio of the through-hole surface area to the total surface area of the thin plate) are determined. Examined.
【００１８】すなわち、走査型電子顕微鏡で薄板表面を
無作為に３０箇所写真撮影（撮影倍率：４００倍）し、
その写真を画像解析装置で処理することにより算出し、
その結果、図１に示すように、全ての細孔２が貫通孔と
なっており、平均細孔径が１０．４μｍ（標準偏差σ：
０．９４）、細孔面積率が２３％の多孔質支持体１が得
られた。That is, the surface of the thin plate was photographed at random in 30 places with a scanning electron microscope (photographing magnification: 400 times).
Calculated by processing the photo with an image analysis device,
As a result, as shown in FIG. 1, all the pores 2 are through holes, and the average pore diameter is 10.4 μm (standard deviation σ:
0.94) and a porous support 1 having a pore area ratio of 23% was obtained.
【００１９】上記レーザ法で製作した多孔質支持体１の
通気抵抗を計測した。測定は常温にて空気を流し単位板
厚当たりの圧力降下を評価する方法で行った。なお、比
較のため従来方法、即ち、金属繊維不織布をベースに圧
延焼結し製作した板厚が１mm、平均細孔径が１０．５μ
ｍ、開口率が２５％の金属繊維・圧延焼結材についても
同様な計測を行った。The airflow resistance of the porous support 1 manufactured by the laser method was measured. The measurement was performed by a method of evaluating the pressure drop per unit plate thickness by flowing air at normal temperature. For comparison, a conventional method, that is, a sheet thickness produced by rolling and sintering a metal fiber nonwoven fabric as a base and having an average pore diameter of 10.5 μm was used.
m, the same measurement was performed for a metal fiber / rolled sintered material having an aperture ratio of 25%.
【００２０】その結果を図２に示すが、従来法のものと
比較して約１／２程度に通気抵抗が減少しており、本発
明法の有効性が確認される。The results are shown in FIG. 2. As shown in FIG. 2, the ventilation resistance is reduced to about one half that of the conventional method, confirming the effectiveness of the method of the present invention.
【００２１】上記の本発明で使用する金属多孔質支持体
１と１０μｍ厚さのＰｄ薄膜３とを重ね合せた。Ｐｄ膜
３の固定方法は種々考えられるが、こゝでは図３に示す
方法で水素ガス分離膜を試作した。すなわち、上記の金
属多孔質支持体１にＰｄ薄膜３を重ね、更に、このＰｄ
薄膜３を固定する支持用リング４を重ね合わせ、この合
わせ部からのガスの漏洩を防止するため、銀ロー５で周
囲を溶接して水素ガス分離膜とした。The porous metal support 1 used in the present invention and the Pd thin film 3 having a thickness of 10 μm were superposed. Although various methods for fixing the Pd membrane 3 are conceivable, here, a hydrogen gas separation membrane was experimentally manufactured by the method shown in FIG. That is, the Pd thin film 3 is overlaid on the metal porous support 1, and
A support ring 4 for fixing the thin film 3 was overlapped, and the periphery was welded with a silver row 5 to form a hydrogen gas separation membrane in order to prevent leakage of gas from this joint.
【００２２】この水素ガス分離膜の水素透過性能を調べ
るため、水素透過試験を行った。試験用の水素ガス分離
膜は図３によって説明したようにして製作したものを図
４のパイプに成形し試験に供した。図４中、１は金属多
孔質支持体、３はＰｄ薄膜、４は支持用リング、５は銀
ロー溶接部を示す。A hydrogen permeation test was performed to examine the hydrogen permeation performance of the hydrogen gas separation membrane. A hydrogen gas separation membrane for a test manufactured as described with reference to FIG. 3 was formed into a pipe shown in FIG. 4 and subjected to a test. In FIG. 4, 1 is a metal porous support, 3 is a Pd thin film, 4 is a support ring, and 5 is a silver-low weld.
【００２３】水素透過試験は図５の試験装置で行った。
即ち、水素ガス分離膜ＡをＯリングＢでステンレス鋼製
外管Ｃに固定し、その外側を電気炉で加熱するようにし
て行った。温度はサーモカップルＤを使用し、内管の中
心部で測定した。The hydrogen permeation test was performed using the test apparatus shown in FIG.
That is, the hydrogen gas separation membrane A was fixed to a stainless steel outer tube C with an O-ring B, and the outside was heated by an electric furnace. The temperature was measured at the center of the inner tube using Thermocouple D.
【００２４】供給孔ＥからＨ2 ／Ｎ2 ＝１（モル）の混
合ガスを連続的に供給し、排出孔Ｆからブリードガスを
排出し、下部の取り出し孔Ｇから水素を得る方式とし
た。なお、Ｈはキャリアガス供給口である。A mixed gas of H 2 / N 2 = 1 (mol) was continuously supplied from the supply hole E, the bleed gas was discharged from the discharge hole F, and hydrogen was obtained from the lower discharge hole G. H is a carrier gas supply port.
【００２５】混合ガスの圧力を３kg／cm2 Ｇ、流量を２
０Ｎｌ／min.で、温度５００℃で試験した結果、９９．
９９％以上の純粋な水素１．４Ｎｌ／min.を得ることが
でき、従来の約１．３倍の性能が得られることを確認し
た。The pressure of the mixed gas is 3 kg / cm 2 G and the flow rate is 2
As a result of a test at a temperature of 500 ° C. at 0 Nl / min.
It was confirmed that 1.4 Nl / min. Of pure hydrogen of 99% or more could be obtained, and that a performance approximately 1.3 times that of the conventional case could be obtained.
【００２６】なお、図６、図７にＰｄ薄膜の他のシール
方法を示す。図６はその断面図、図７はその外観図であ
る。その方法を図６によって説明する。まず圧延等にて
均一厚みでしかも２〜３μｍ厚まで薄膜化したＰｄを含
む金属、すなわちＰｄ薄膜３の外周部をプレス加工等で
ビード状に成形し、ビード状部３′を形成させる。金属
多孔質支持体１は１８−８ステンレス鋼（ＳＵＳ３０４
材）の薄板表面に、微細なスポットに集光でき、金属材
料に対する反射率の小さいＹＡＧレーザを細孔径（１０
μｍ径程度）となるよう出力調整、照射し細孔２を加工
してある。FIGS. 6 and 7 show another sealing method of the Pd thin film. FIG. 6 is a sectional view, and FIG. 7 is an external view thereof. The method will be described with reference to FIG. First, a metal containing Pd having a uniform thickness by rolling or the like and thinned to a thickness of 2 to 3 μm, that is, an outer peripheral portion of the Pd thin film 3 is formed into a bead shape by press working or the like to form a bead-shaped portion 3 ′. The metal porous support 1 is made of 18-8 stainless steel (SUS304).
A YAG laser that can focus light into a fine spot on the surface of a thin plate of
The pores 2 are processed by adjusting the output and irradiating so as to have a diameter of about μm.
【００２７】上記Ｐｄ薄膜３をこの金属多孔質支持体１
に貼り合わせ、ガスもれを防止するため端部外周を溶接
（ろう付等）５する。The Pd thin film 3 is coated on the metal porous support 1
Then, the outer periphery of the end is welded (brazed or the like) 5 to prevent gas leakage.
【００２８】その後、ＹＡＧレーザで細孔加工した比較
的板厚の厚いカバー（ＳＵＳ３０４材）１′に、前記金
属多孔質支持体１の細孔２とカバー１′の細孔２′とが
合致するよう貼り合わせたのち、端部外周を溶接５し、
ガスもれを防止するとともに両者を固定する。Thereafter, the pores 2 of the metal porous support 1 and the pores 2 'of the cover 1' coincide with the relatively thick cover (SUS304 material) 1 'which has been subjected to pore processing with a YAG laser. After welding, the outer periphery of the end is welded 5
Prevent gas leakage and fix both.
【００２９】さらにＰｄ薄膜３の上面側に、同様に細孔
２が加工されたＳＵＳ３０４材のカバー１″を貼り合
せ、前記のカバー１′と溶接加工５する。図６において
原料ガスＧは図示のようにＰｄ薄膜３側から供給され、
下方のカバー１′の細孔２′より水素Ｈ2 が透過され
る。Further, a cover 1 ″ of SUS304 material similarly processed with pores 2 is attached to the upper surface side of the Pd thin film 3, and the cover 1 ′ is welded 5. The raw material gas G is shown in FIG. Is supplied from the Pd thin film 3 side as in
Hydrogen H 2 is transmitted through the pores 2 ′ of the lower cover 1 ′.
【００３０】このように構成された水素分離膜は図７の
ような外観となり、細孔２のある部分がガス供給部とな
る。このような外観の水素分離膜を分離装置構成に応じ
て円筒化したり、箱形あるいは平板形に加工して使用す
る。The hydrogen separation membrane thus configured has an appearance as shown in FIG. 7, and the portion having the pores 2 serves as a gas supply unit. The hydrogen separation membrane having such an appearance is formed into a cylinder or processed into a box shape or a plate shape according to the configuration of the separation apparatus.
【００３１】（参考例２） 供試材として１８−８ステンレス鋼（ＪＩＳ規格：ＳＵ
Ｓ３０４）の薄板（１０ｍｍ×１０ｍｍ×０．０１ｍ
ｍ）を用い、エッチング法による孔明け試験を下記手順
にて実施した。 Reference Example 2 18-8 stainless steel (JIS standard: SU) was used as a test material.
S304) thin plate (10 mm × 10 mm × 0.01 m)
Using m), a drilling test by an etching method was performed according to the following procedure.
【００３２】（１）供試材表面に、１〜２μｍ厚さの紫
外線硬化型のレジストを塗布し、乾燥後にあらかじめ所
定のパターンを形成させたフィルムを貼付けた。(1) A UV-curable resist having a thickness of 1 to 2 μm was applied to the surface of the test material, and after drying, a film on which a predetermined pattern had been formed was pasted.
【００３３】（２）このフィルム上から紫外光を照射
し、レジストを硬化させた後、水洗し、フィルム及び非
硬化部のレジストを除去した。(2) The film was irradiated with ultraviolet light to cure the resist, and then washed with water to remove the film and the uncured portion of the resist.
【００３４】（３）この後、塩化第２鉄溶液を用いて非
硬化部をエッチングし、孔明け処理を行った。なお、塩
化第２鉄溶液の温度は約５０℃、エッチング時間は約２
分とした。(3) Thereafter, the non-cured portion was etched using a ferric chloride solution to perform a hole-piercing treatment. The temperature of the ferric chloride solution was about 50 ° C., and the etching time was about 2 hours.
Minutes.
【００３５】この結果、孔ピッチ：８０μｍ、孔径：６
０μｍ、開孔率：５０％の微細孔の加工ができることを
確認した。As a result, the hole pitch: 80 μm and the hole diameter: 6
It was confirmed that micropores with a pore size of 0 μm and an opening ratio of 50% could be processed.
【００３６】（参考例３） 以下、図８、図９及び図１０によって、本発明の一参考
例を説明する。図８はここで使用する多孔質金属支持体
１の平面図を、図９はその断面図を示し、図１０は水素
ガス分離膜の構成の断面図である。 Reference Example 3 Hereinafter, a reference example of the present invention will be described with reference to FIGS. 8, 9 and 10. 8 is a plan view of the porous metal support 1 used here, FIG. 9 is a cross-sectional view thereof, and FIG. 10 is a cross-sectional view of the structure of the hydrogen gas separation membrane.
【００３７】金属材料としては１８−８ステンレス鋼
（ＳＵＳ３０４）薄板を使用した。この薄板（板厚１m
m）の表面に微細なスポットに集光でき、金属材料に対
する反射率の小さなＹＡＧレーザを細孔径１０μｍ、細
孔面積率が４０％となるように出力調整、照射し、金属
多孔質支持体１を製作し、その細孔２の径の大きさ、面
積率を調べた。As the metal material, a thin plate of 18-8 stainless steel (SUS304) was used. This thin plate (plate thickness 1m
m), a YAG laser capable of condensing light into a fine spot on the surface and having a small reflectance to the metal material is output-adjusted and irradiated so that the pore diameter becomes 10 μm and the pore area ratio becomes 40%. Was manufactured, and the size and area ratio of the pores 2 were examined.
【００３８】すなわち、走査型電子顕微鏡で薄板表面を
４００倍拡大し、その写真を画像解析装置で処理して調
査した。その結果全てが貫通孔となっており、平均細孔
径が１０．４μｍ、細孔面積率４１％の多孔質支持体１
が得られていた。That is, the surface of the thin plate was magnified 400 times with a scanning electron microscope, and the photograph was processed by an image analyzer and examined. As a result, all of the porous support 1 had through holes, an average pore diameter of 10.4 μm, and a pore area ratio of 41%.
Was obtained.
【００３９】板厚１mmに約１０μｍ径の細孔が得られた
ことから、次の手段で水素ガス分離膜の製作を行った。Since pores having a diameter of about 10 μm were obtained at a plate thickness of 1 mm, a hydrogen gas separation membrane was manufactured by the following means.
【００４０】（１）板厚１０μｍのＳＵＳ３０４材を１
００枚重ねて同時に１０μｍ径の細孔をレーザ加工し、
金属多孔質支持体１を製作した。(1) One SUS304 material having a thickness of 10 μm
Laser processing of 10 μm diameter pores at the same time
A metal porous support 1 was produced.
【００４１】（２）板厚７０μｍのＳＵＳ３０４材を１
４枚重ねて同時に１５μｍ径の細孔をレーザ加工し、金
属多孔質支持体１′を製作した。(2) SUS304 material having a thickness of 70 μm
Four sheets were laminated and simultaneously laser-processed the pores having a diameter of 15 μm to produce a metal porous support 1 ′.
【００４２】（３）板厚０．５mmのＳＵＳ３０４材を２
枚重ねて３０μｍ径の細孔をレーザ加工し、金属多孔質
支持体１″を製作した。(3) SUS304 material having a thickness of 0.5 mm
Laser processing was performed on the fine pores having a diameter of 30 μm by stacking to form a metal porous support 1 ″.
【００４３】（４）上記で得られた種々板厚、細孔径の
金属多孔質支持体を図１０に示すように、Ｐｄ薄膜３を
はさみこむように貼り合わせた。Ｐｄ薄膜３は圧延加工
で得られた２〜３μｍの均一厚みを有するものであり、
これを金属多孔体１で両面からはさみこんで貼り合わせ
る。その後一方向に順次多層状に貼り合わせてゆく方式
である。(4) The metal porous supports of various thicknesses and pore diameters obtained as described above were bonded so as to sandwich the Pd thin film 3 as shown in FIG. The Pd thin film 3 has a uniform thickness of 2 to 3 μm obtained by rolling,
This is sandwiched from both sides with the porous metal body 1 and bonded. After that, it is a method in which the layers are sequentially laminated in one direction in a multilayer shape.
【００４４】Ｐｄ薄膜３の両面に金属多孔質支持体１を
設けた理由は、原料ガス供給側に配される触媒が直接Ｐ
ｄ薄膜３に接し、Ｐｄ薄膜３が損傷するのを防止するも
のであるが、上記のようにすることにより水素分離性能
が低下することはない。The reason for providing the metal porous support 1 on both sides of the Pd thin film 3 is that the catalyst disposed on the source gas supply side is directly
The contact with the d thin film 3 prevents the Pd thin film 3 from being damaged. However, the above-described operation does not lower the hydrogen separation performance.
【００４５】さらにＰｄ薄膜３は圧延加工した均一厚み
の２〜３μｍ厚のＰｄ含有材を用いているので、従来の
メッキ法の１／５〜１／１０厚みとなり、その分だけで
も水素透過性能が向上する。Further, since the Pd thin film 3 is made of a rolled Pd-containing material having a uniform thickness of 2 to 3 μm, the Pd thin film 3 has a thickness of 1/5 to 1/10 that of the conventional plating method. Is improved.
【００４６】また、金属多孔質支持体も板厚方向に直線
的細孔となっているので原料ガスの流入がスムーズ、か
つ分離水素の透過もスムーズとなり、従来より１／３〜
１／５倍の透過抵抗となった。Further, since the metal porous support also has linear pores in the plate thickness direction, the flow of the raw material gas is smooth, and the permeation of the separated hydrogen is also smooth.
The transmission resistance was ５ times.
【００４７】細孔径および細孔面積率は自由に調整加工
できるので目的に応じた膜が製作できる。特にエッチン
グ方法による穿孔は、孔径が板厚に律則されるため、微
細孔を得るためには、微小板厚の薄板が必要であり、こ
れはＰｄ薄膜の支持体としては強度的に不充分となる。
このため上記のようにした多層支持体は支持体の強度ア
ップに有効である。Since the pore diameter and the pore area ratio can be freely adjusted and processed, a membrane suitable for the purpose can be manufactured. In particular, in the case of drilling by the etching method, since the hole diameter is determined by the plate thickness, a thin plate having a small plate thickness is necessary to obtain fine holes, which is insufficient in strength as a support for the Pd thin film. Becomes
Therefore, the multilayer support as described above is effective for increasing the strength of the support.
【００４８】（実施例１） 金属多孔質支持体に、Ｐｄ薄膜を貼り合せた、水素ガス
分離膜の高温条件下での耐久性、すなわち、長期間使用
した場合にステンレス鋼母材とＰｄの拡散合金化による
性能低下が懸念されるため、この相互拡散防止を計る目
的で、図１１に示すように、バリア層６をステンレス鋼
よりなる金属多孔質支持体１とＰｄ薄膜３との間に介在
させた水素ガス分離膜を作製した。(Example 1 ) The durability of a hydrogen gas separation membrane obtained by bonding a Pd thin film to a metal porous support under high-temperature conditions, that is, when a stainless steel base material and Pd were used for a long period of time. Since there is a concern that the performance may be degraded due to the diffusion alloying, the barrier layer 6 is placed between the metal porous support 1 made of stainless steel and the Pd thin film 3 as shown in FIG. A hydrogen gas separation membrane interposed was produced.
【００４９】すなわち、バリア層６として、ＴｉＮを選
定し、熱ＣＶＤ法により約２μｍの厚さで金属多孔質支
持体（２０mm×５０mm×１mm，平均孔径：１０μｍ，細
孔面積率：２０％）１上に成膜させ、その後１０μｍ厚
さのＰｄ薄膜３を貼り合せたものを作製し、長期間使用
による性能評価を実施した。なお、比較のためバリア層
を実施しないものについても、長期間使用による性能評
価を行った。That is, TiN is selected as the barrier layer 6, and a metal porous support (20 mm × 50 mm × 1 mm, average pore diameter: 10 μm, pore area ratio: 20%) is formed by thermal CVD at a thickness of about 2 μm. Then, a Pd thin film 3 having a thickness of 10 μm was laminated on the substrate 1, and a performance evaluation was performed over a long period of use. For comparison, performance evaluation was also performed on a device without a barrier layer after long-term use.
【００５０】この性能評価は既に述べた図５の装置で、
混合ガスの圧力：３kg／cm2 Ｇ，流量：２０Ｎｌ／min
，温度：５００℃で実施したが、バリア層を介在させ
たものは１５００時間運転後においても性能低下は殆ど
ないが、バリア層を実施しないものでは水素透過量が約
１／２に低下することが判明した。なお、バリア層はＴ
ｉＮに限らず、他のセラミックや金属酸化物でもよい。This performance evaluation was performed using the apparatus shown in FIG.
Pressure of mixed gas: 3 kg / cm 2 G, flow rate: 20 Nl / min
, Temperature: 500 ° C., with the barrier layer interposed, there is almost no performance decrease even after operation for 1500 hours, but without the barrier layer, the hydrogen permeation amount is reduced to about ２. There was found. The barrier layer is made of T
Not limited to iN, other ceramics or metal oxides may be used.
【００５１】[0051]
【発明の効果】本発明によれば次の効果が奏される。 （１）金属多孔質支持体およびこれの支持カバーに設け
てある細孔は板厚方向にほぼ直線であり、水素分離抵抗
が小さくなる。 （２）Ｐｄ薄膜にビードを設けると、熱膨張、変形にビ
ードが対処するのでＰｄ薄膜の損傷が防止できる。 （３）Ｐｄ薄膜へのガス供給側に保護カバーを設けてあ
るので、ガス圧力や触媒接触等によるＰｄ薄膜の損傷防
止ができる。 （４）完全シール体となっているため種々形状へ変形加
工できる。 （５）Ｐｄ薄膜が従来メッキ法より１／５〜１／１０と
薄く、均一にできるので水素透過率が向上し、高純度な
水素が得られる。 （６）Ｐｄ薄膜と金属多孔質支持体の間にバリア層を設
けているので、水素ガス分離膜の劣化を防止することが
できる。According to the present invention, the following effects can be obtained. (1) The pores provided in the metal porous support and its support cover are substantially straight in the plate thickness direction, and the hydrogen separation resistance is reduced. (2) When a bead is provided on the Pd thin film, the bead copes with thermal expansion and deformation, so that damage to the Pd thin film can be prevented. (3) Since the protective cover is provided on the gas supply side to the Pd thin film, it is possible to prevent the Pd thin film from being damaged by gas pressure, catalyst contact, or the like. (4) Since it is a completely sealed body, it can be deformed into various shapes. (5) Since the Pd thin film can be made as thin as 1/5 to 1/10 of the conventional plating method and uniform, the hydrogen permeability is improved and high-purity hydrogen can be obtained. (6) Since the barrier layer is provided between the Pd thin film and the metal porous support, it is possible to prevent deterioration of the hydrogen gas separation membrane.
【図１】本発明で使用する金属多孔質支持体及びそれに
重ね合せたＰｄ膜の状態を示す説明図FIG. 1 is an explanatory view showing a state of a metal porous support used in the present invention and a Pd film superposed thereon.
【図２】本発明で使用する金属多孔質支持体と従来の金
属組織不織布を圧延焼結した支持体の通気抵抗の比較図FIG. 2 is a comparison diagram of the air flow resistance between a metal porous support used in the present invention and a support obtained by rolling and sintering a conventional metal structure nonwoven fabric.
【図３】金属多孔質支持体とＰｄ薄膜の重ね合せの一方
法の説明図FIG. 3 is an explanatory view of one method of superposing a metal porous support and a Pd thin film.
【図４】図３で得られた水素ガス分離膜の水素透過性を
調べるために製作した水素ガス分離膜の説明図FIG. 4 is an explanatory view of a hydrogen gas separation membrane manufactured for examining the hydrogen permeability of the hydrogen gas separation membrane obtained in FIG.
【図５】図４の水素ガス分離膜の水素透過性を調べるた
めの試験装置の説明図FIG. 5 is an explanatory view of a test apparatus for examining the hydrogen permeability of the hydrogen gas separation membrane of FIG.
【図６】金属多孔質支持体とＰｄ薄膜の重ね合せの他の
方法の説明のための断面図FIG. 6 is a cross-sectional view for explaining another method of laminating a metal porous support and a Pd thin film.
【図７】図６の外観図FIG. 7 is an external view of FIG. 6;
【図８】本発明の一参考例で使用する金属多孔質支持体
の平面図FIG. 8 is a plan view of a metal porous support used in one reference example of the present invention.
【図９】図８の断面図FIG. 9 is a sectional view of FIG. 8;
【図１０】本発明の一参考例の水素ガス分離膜の構成の
断面図FIG. 10 is a cross-sectional view of a configuration of a hydrogen gas separation membrane according to a reference example of the present invention.
【図１１】バリア層を介在させた本発明の一実施例の水
素ガス分離膜の構成の断面図FIG. 11 is a cross-sectional view of a configuration of a hydrogen gas separation membrane of one embodiment of the present invention with a barrier layer interposed.
【図１２】従来の水素ガス分離膜の欠点の説明図FIG. 12 is an explanatory view of a defect of a conventional hydrogen gas separation membrane.
フロントページの続き (72)発明者 湯崎 芳啓 広島市西区観音新町四丁目６番22号 三 菱重工業株式会社広島研究所内 (72)発明者 末田 穰 広島市西区観音新町四丁目６番22号 三 菱重工業株式会社広島研究所内 (72)発明者 ▲吉▼田 康之 広島市西区観音新町四丁目６番22号 三 菱重工業株式会社広島研究所内 (72)発明者 梶原 哲雄 広島市西区観音新町四丁目６番22号 三 菱重工業株式会社広島研究所内 (72)発明者 石橋 保博 広島市西区観音新町四丁目６番22号 三 菱重工業株式会社広島研究所内 (72)発明者 飯伏 順一 広島市西区観音新町四丁目６番22号 三 菱重工業株式会社広島研究所内 (56)参考文献 特開 昭62−121616（ＪＰ，Ａ) 特開 平１−262924（ＪＰ，Ａ) 特開 平１−218607（ＪＰ，Ａ) 特開 平１−262903（ＪＰ，Ａ) 特開 昭53−95314（ＪＰ，Ａ) 特開 昭62−129106（ＪＰ，Ａ) 特開 平３−288534（ＪＰ，Ａ) 特開 平４−346824（ＪＰ，Ａ) 特開 昭61−157326（ＪＰ，Ａ) 特開 平４−349926（ＪＰ，Ａ) 特開 昭49−127874（ＪＰ，Ａ) 特開 平５−76737（ＪＰ，Ａ) 特公 昭44−15283（ＪＰ，Ｂ１) 特公 昭49−48834（ＪＰ，Ｂ１) (58)調査した分野(Int.Cl.6，ＤＢ名) B01D 71/02 B23K 26/00 C01B 3/56 Continuing from the front page (72) Inventor Yoshihiro Yuzaki 4-6-22 Kannon Shinmachi, Nishi-ku, Hiroshima City Inside the Hiroshima Laboratory, Rishiju Heavy Industries Co., Ltd. (72) Inventor Joi Sueda 4-6-22 Kanon Shinmachi, Nishi-ku, Hiroshima City 3 Inside the Hiroshima Research Laboratory, Hishi Heavy Industries Co., Ltd. No. 6-22 Sanyo Heavy Industries Co., Ltd.Hiroshima Research Center (72) Inventor Yasuhiro Ishibashi 4-2-2 Kanon Shinmachi, Nishi-ku, Hiroshima City Within Sanishi Heavy Industries Co., Ltd.Hiroshima Research Center (72) Inventor Junichi Iibushi Kannon, Nishi-ku, Hiroshima City No. 6-22 Shinmachi, Hiroshima Laboratory, Mitsubishi Heavy Industries, Ltd. (56) References JP-A-62-121616 (JP, A) JP-A-1-262924 (JP, A) JP-A-1-218607 (JP) JP-A-1-262903 (JP, A) JP-A-53-95314 (JP, A) JP-A-62-1291 06 (JP, A) JP-A-3-288534 (JP, A) JP-A-4-346824 (JP, A) JP-A-61-157326 (JP, A) JP-A-4-349926 (JP, A) JP-A-49-127874 (JP, A) JP-A-5-76737 (JP, A) JP-B-44-15283 (JP, B1) JP-B-49-48834 (JP, B1) (58) (Int.Cl. 6 , DB name) B01D 71/02 B23K 26/00 C01B 3/56
Claims (1)
工した金属多孔質支持体の表面に、Ｐｄを含有する薄膜
を重ね合わせ、前記金属多孔質支持体とＰｄを含有する
薄膜との間に薄層のバリア層を介在させてなることを特
徴とする水素ガス分離膜。1. A thin film containing Pd is superposed on the surface of a porous metal support formed by drilling by a laser method or etching , and the porous support and Pd are contained.
A hydrogen gas separation membrane comprising a thin barrier layer interposed between the thin film and a thin film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3245430A JP2960998B2 (en) | 1991-09-25 | 1991-09-25 | Hydrogen gas separation membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3245430A JP2960998B2 (en) | 1991-09-25 | 1991-09-25 | Hydrogen gas separation membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0576738A JPH0576738A (en) | 1993-03-30 |
| JP2960998B2 true JP2960998B2 (en) | 1999-10-12 |
Family
ID=17133545
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3245430A Expired - Lifetime JP2960998B2 (en) | 1991-09-25 | 1991-09-25 | Hydrogen gas separation membrane |
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| Country | Link |
|---|---|
| JP (1) | JP2960998B2 (en) |
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| JP2012193097A (en) * | 2011-03-18 | 2012-10-11 | Panasonic Corp | Hydrogen generator |
-
1991
- 1991-09-25 JP JP3245430A patent/JP2960998B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102378644A (en) * | 2009-04-07 | 2012-03-14 | 林德股份公司 | Diaphragm pipe and reactor having a diaphragm pipe |
| US8753433B2 (en) | 2009-04-07 | 2014-06-17 | Plansee Se | Membrane tube and reactor having a membrane tube |
| CN102378644B (en) * | 2009-04-07 | 2014-11-26 | 普兰西公司 | Diaphragm pipe and reactor having a diaphragm pipe |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0576738A (en) | 1993-03-30 |
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