JP3373006B2 - Manufacturing method of hydrogen separation membrane - Google Patents
Manufacturing method of hydrogen separation membraneInfo
- Publication number
- JP3373006B2 JP3373006B2 JP25500493A JP25500493A JP3373006B2 JP 3373006 B2 JP3373006 B2 JP 3373006B2 JP 25500493 A JP25500493 A JP 25500493A JP 25500493 A JP25500493 A JP 25500493A JP 3373006 B2 JP3373006 B2 JP 3373006B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- membrane
- thin film
- hydrogen
- hollow fiber
- 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 - Fee Related
Links
- 239000012528 membrane Substances 0.000 title claims description 75
- 239000001257 hydrogen Substances 0.000 title claims description 40
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 40
- 238000000926 separation method Methods 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 title claims 3
- 239000010408 film Substances 0.000 claims description 49
- 239000010409 thin film Substances 0.000 claims description 36
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 23
- 239000011148 porous material Substances 0.000 claims description 23
- 239000000919 ceramic Substances 0.000 claims description 22
- 229910001252 Pd alloy Inorganic materials 0.000 claims description 13
- 238000003980 solgel method Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 58
- 239000012510 hollow fiber Substances 0.000 description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 32
- 150000002431 hydrogen Chemical class 0.000 description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 229910002070 thin film alloy Inorganic materials 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910001179 chromel Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- CVSVTCORWBXHQV-UHFFFAOYSA-N creatine Chemical compound NC(=[NH2+])N(C)CC([O-])=O CVSVTCORWBXHQV-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 1
- 239000005394 sealing glass Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Hydrogen, Water And Hydrids (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、水素分離膜の製造法に
関する。更に詳しくは、水素選択透過性膜を形成させた
多孔質セラミックス膜よりなる水素分離膜の製造法に関
する。TECHNICAL FIELD The present invention relates to a method for producing a hydrogen separation membrane . More specifically, the present invention relates to a method for producing a hydrogen permeable membrane, which is made of a porous ceramic membrane having a hydrogen selective permeable membrane.
【０００２】[0002]
【従来の技術】水素の超高純度精製用膜として、Pd-Ag
合金膜が知られており(Sep．Sci．Technol．第22巻第87
3〜887頁、1987年)、既に実用化もされている。このよ
うな水素分離用Pd系合金膜は、従来合金単独で中空状に
作られており、従って、それの強度上の制約から、外径
が1.6mmのもので最小膜厚が約80μm程度が限界であり、
水素透過速度は膜厚に逆比例するため、水素透過速度が
遅いという問題がみられた。2. Description of the Related Art Pd-Ag is used as a membrane for ultra-high purity purification of hydrogen.
Alloy films are known (Sep. Sci. Technol. Vol. 22, Vol. 87).
3 to 887, 1987), which has already been put to practical use. Such a Pd-based alloy membrane for hydrogen separation is conventionally made of a single alloy in a hollow shape.Therefore, due to its strength limitation, the outer diameter is 1.6 mm and the minimum thickness is about 80 μm. Is the limit,
Since the hydrogen permeation rate is inversely proportional to the film thickness, there was a problem that the hydrogen permeation rate was slow.
【０００３】その対策として、多孔質アルミナチューブ
表面に、化学メッキ法でPd系合金膜を形成させる方法が
提案されているが(J．Memb．Sci．第56巻第303、315
頁、1991年)、膜厚については4.5〜6.4μmと改善されて
はいるものの未だ厚く、しかも膜形成プロセスが複雑
で、工程が多いという難点がみられる。更に、水素雰囲
気下で加熱・冷却のサイクルをくり返すと、水素脆性に
より膜が劣化するという問題がみられ、これは水素分離
膜として使用する上で、絶対に見逃すことのできない問
題である。As a countermeasure, a method of forming a Pd-based alloy film on the surface of a porous alumina tube by a chemical plating method has been proposed (J. Memb. Sci. 56, 303, 315).
(Page, 1991), the film thickness has been improved to 4.5 to 6.4 μm, but it is still thick, and the film forming process is complicated and there are many problems. Further, when the heating / cooling cycle is repeated in a hydrogen atmosphere, there is a problem that the membrane deteriorates due to hydrogen embrittlement, which is a problem that cannot be overlooked when used as a hydrogen separation membrane.
【０００４】そこで、Pd-Ag合金膜を水素選択透過性膜
とする水素分離膜であって、このPd系合金膜を薄膜とし
て形成させることにより、水素透過速度を高めたもの、
具体的には、多孔質セラミックス中空糸外表面上に、Pd
(NO3)2-AgNO3混合物水溶液の噴霧熱分解物たるPd-Ag合
金薄膜を堆積させて製造される水素分離膜が、本発明者
の一部らによって提案されており、そこでは膜厚約2μm
で500℃におけるH2/N2分離係数24、水素透過係数8×10
-7モル/m2・s・PaのPd-Ag合金薄膜が形成されている(化
学工学会第25回秋季大会研究発表講演要旨集第1分冊第7
頁、1992年)。Therefore, a hydrogen separation membrane having a Pd-Ag alloy membrane as a hydrogen selective permeable membrane, in which this Pd-based alloy membrane is formed as a thin film to enhance the hydrogen permeation rate,
Specifically, on the outer surface of the porous ceramic hollow fiber, Pd
A hydrogen separation membrane produced by depositing a Pd-Ag alloy thin film, which is a spray pyrolysate of (NO 3 ) 2 -AgNO 3 mixture aqueous solution, has been proposed by some of the present inventors, where the film thickness is About 2 μm
H 2 / N 2 separation factor at 500 ℃ at 24, hydrogen permeation coefficient 8 × 10
-7 mol / m 2 · s · Pa Pd-Ag alloy thin film is formed (Proceedings of the 25th Autumn Meeting of the Chemical Engineering Society of Japan
P., 1992).
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、Pd薄
膜またはPd合金薄膜よりなる水素選択透過性膜を多孔質
セラミックス膜の細孔内に形成させることにより薄膜化
を図り、これにより水素透過性を更に改善させた水素分
離膜の製造法を提供することにある。An object of the present invention is to achieve a thin film by forming a hydrogen selective permeable film composed of a Pd thin film or a Pd alloy thin film in the pores of a porous ceramics film. Hydrogen content with further improved permeability
It is to provide a method for manufacturing a separation membrane .
【０００６】[0006]
【課題を解決するための手段】本発明により、細孔内に
Pd薄膜またはPd合金薄膜を形成させた多孔質セラミック
ス膜よりなる水素分離膜が、多孔質セラミックス膜の両
側に圧力差を設け、気化させたPd膜源またはPd合金膜源
を多孔質セラミックス膜の細孔内に吸引しながら、細孔
内でPd膜化またはPd合金膜化させることにより製造され
る。According to the present invention, in the pores
A hydrogen separation membrane consisting of a porous ceramics film on which a Pd thin film or Pd alloy thin film is formed, a pressure difference is provided on both sides of the porous ceramics film, and the vaporized Pd film source or Pd alloy film source It is manufactured by forming a Pd film or a Pd alloy film in the pores while sucking into the pores.
【０００７】支持体として用いられる多孔質セラミック
ス膜としては、一般に平均細孔率が約20〜60%、好まし
くは約40〜60%であって、平均細孔径が約5〜5000nm、好
ましくは約50〜500nmの精密ロ過性能を有する、α-アル
ミナ、シリカ、ジルコニア等のセラミックスあるいはこ
れらの複合物または混合物から形成された多孔質膜など
が用いられる。膜の形状は、一般に中空糸膜であること
が好ましいが、この他にフィルム状乃至シート状のもの
なども用いられる。The porous ceramic membrane used as a support generally has an average porosity of about 20 to 60%, preferably about 40 to 60%, and an average pore diameter of about 5 to 5000 nm, preferably about A porous film formed of a ceramic such as α-alumina, silica, zirconia, or a composite or mixture thereof having a precision filtration performance of 50 to 500 nm is used. Generally, the shape of the membrane is preferably a hollow fiber membrane, but in addition to this, a film-like or sheet-like one may be used.
【０００８】また、多孔質セラミックス膜は、その表面
にゾル・ゲル法によるγ-アルミナ薄膜を形成させて用
いることができる。ゾル・ゲル法によるγ-アルミナ薄
膜の形成は、アルミニウムイソプロポキシドを加水分解
後、酸で解こうすることにより調製したベーマイトゾル
を用い、これを多孔質セラミックス膜にディップコーテ
ィング(引上げ速度0.5〜2.0mm/秒)することによりベー
マイトゲル膜を形成させ、これを室温下で一夜乾燥させ
た後、約400〜800℃で約5〜10時間焼成する操作を、１
回以上、一般には複数回くり返すことにより行われる。The porous ceramic film can be used by forming a γ-alumina thin film on the surface thereof by the sol-gel method. The γ-alumina thin film is formed by the sol-gel method using a boehmite sol prepared by hydrolyzing aluminum isopropoxide and then deflocculating it with an acid. (2.0 mm / sec) to form a boehmite gel film, which is dried overnight at room temperature and then calcined at about 400 to 800 ° C. for about 5 to 10 hours.
Repeated more than once, generally multiple times.
【０００９】このような多孔質セラミックス膜の細孔内
へのPd薄膜またはPd合金薄膜の形成は、膜の両側に圧力
差を設け、気化させたPd膜源またはPd合金膜源を多孔質
セラミックス膜の細孔内に吸引しながら、細孔内でPd膜
化またはPd合金膜化させることにより行われる。The formation of the Pd thin film or the Pd alloy thin film in the pores of such a porous ceramic film is performed by providing a pressure difference on both sides of the film to vaporize the vaporized Pd film source or Pd alloy film source into the porous ceramic film. It is carried out by forming a Pd film or a Pd alloy film in the pores while sucking into the pores of the membrane.
【００１０】Pd膜源としては、一般に酢酸パラジウム、
塩化パラジウム、硝酸パラジウム等の金属塩が用いら
れ、これを熱分解させてPd薄膜を形成させるCVD法(化学
蒸着法)が適用される。Pd膜源としては熱分解によりPd
を生成するものであれば、金属塩以外のものも用いるこ
とができる。更に、Ag、Au、Pt、Rh、Ru、Ir等と合金化
してもよく、その場合にはそれらの金属源として、金属
塩等の内熱分解でそれぞれの金属を生成するものが使用
される。その際、Pd源と熱分解温度の近いものを用いる
ことが好ましい。As a Pd film source, in general, palladium acetate,
A metal salt such as palladium chloride or palladium nitrate is used, and a CVD method (chemical vapor deposition method) in which the metal salt is thermally decomposed to form a Pd thin film is applied. As a Pd film source, Pd
Other than metal salts can also be used as long as they can produce. Further, it may be alloyed with Ag, Au, Pt, Rh, Ru, Ir, etc., and in that case, as the metal source thereof, those which generate respective metals by internal thermal decomposition of metal salts are used. . At that time, it is preferable to use a Pd source having a thermal decomposition temperature close to that of the Pd source.
【００１１】このCVD法を多孔質セラミックス中空糸膜
について適用する場合には、図１に示されるような装置
を用いて行われる。When this CVD method is applied to a porous ceramic hollow fiber membrane, it is carried out using an apparatus as shown in FIG.
【００１２】反応器１底部の細径部にOリング２によっ
て多孔質セラミックス中空糸膜３を固定し、その上端部
をガラス(例えば、Na2O-B2O3-SiO2系ガラス)で封止４す
る。中空糸膜３内のガスは、中空糸膜の開口端５より、
ロータリポンプ６で連続的に排気される。また、反応器
１内のガスは、ロータリポンプ７により排気される。こ
れら反応器１および中空糸膜３の出口の圧力は、ピラニ
ゲージ８および９によってそれぞれ測定され、排気量は
石けん膜流量計で測定する。The porous ceramic hollow fiber membrane 3 is fixed to the small diameter portion at the bottom of the reactor 1 by the O-ring 2, and the upper end portion thereof is sealed with glass (for example, Na 2 OB 2 O 3 -SiO 2 glass). 4. The gas in the hollow fiber membrane 3 flows from the open end 5 of the hollow fiber membrane,
It is continuously exhausted by the rotary pump 6. The gas in the reactor 1 is exhausted by the rotary pump 7. The pressures at the outlets of the reactor 1 and the hollow fiber membrane 3 are measured by Pirani gauges 8 and 9, respectively, and the exhaust gas amount is measured by a soap membrane flow meter.
【００１３】反応器１内には、アルゴンガス導入管10に
より、流量制御器11を通して、アルゴンガスが供給さ
れ、例えばPd膜源として酢酸パラジウムを用い、また多
孔質セラミックス膜として平均細孔径約150nm、平均細
孔率約40%の多孔質α-アルミナ中空糸膜を用いた場合、
その圧力は約20〜2000Pa、好ましくは約150〜200Paに保
たれる。一方、中空糸膜３内の圧力は約1〜100Pa、好ま
しくは約6〜9Paに保たれ、例えばアルゴンガスの供給量
が6ml/分(STP)の場合、排気量は約0.2〜0.3ml/分(STP)
である。なお、圧力および圧力差は、Pd膜源またはPd合
金膜源の特性や多孔質セラミックス膜の特性によって異
なり、一概には特定できないが、一般には約10〜2000Pa
程度の範囲内の適当な値が選ばれる。反応器１は、温度
制御器付きの電気炉12により外部から加熱され、その温
度はアルメル・クロメル熱電対13によって検出される。Argon gas is supplied into the reactor 1 through an argon gas introduction pipe 10 through a flow rate controller 11. For example, palladium acetate is used as a Pd film source, and an average pore diameter is about 150 nm as a porous ceramic film. , When using a porous α-alumina hollow fiber membrane with an average porosity of about 40%,
The pressure is kept at about 20-2000 Pa, preferably about 150-200 Pa. On the other hand, the pressure in the hollow fiber membrane 3 is maintained at about 1 to 100 Pa, preferably about 6 to 9 Pa. For example, when the supply amount of argon gas is 6 ml / min (STP), the exhaust amount is about 0.2 to 0.3 ml / Minute (STP)
Is. The pressure and the pressure difference differ depending on the characteristics of the Pd film source or the Pd alloy film source and the characteristics of the porous ceramics film, and cannot be specified unconditionally, but generally about 10 to 2000 Pa.
A suitable value within the range of degree is selected. The reactor 1 is externally heated by an electric furnace 12 having a temperature controller, and its temperature is detected by an alumel-chromel thermocouple 13.
【００１４】Pd膜源物質またはPd合金膜源物質14は、反
応器１の本体底部15に置かれ、上記のような排気条件下
で、約300〜500℃に加熱される。このような反応温度に
約1〜3時間程度保持すると、熱分解で生じたPdまたはPd
合金は多孔質セラミックス中空糸膜３の外表面側の細孔
内に担持され、そこにPd薄膜またはPd合金薄膜を形成さ
せる。The Pd film source material or Pd alloy film source material 14 is placed on the bottom 15 of the body of the reactor 1 and heated to about 300-500 ° C. under the exhaust conditions as described above. If the reaction temperature is maintained for about 1 to 3 hours, Pd or Pd generated by thermal decomposition
The alloy is carried in the pores on the outer surface side of the porous ceramic hollow fiber membrane 3 to form a Pd thin film or a Pd alloy thin film there.
【００１５】[0015]
【発明の効果】本発明により、細孔内にPd薄膜またはPd
合金薄膜よりなる水素選択透過性膜を形成させた多孔質
セラミックス膜よりなる水素分離膜の製造法が提供され
る。ここで多孔質セラミックス膜の細孔内に形成された
Pd薄膜またはPd合金薄膜は、ピンホールがなく、水素選
択透過性および水素透過速度の点でもすぐれ、しかも水
素分離膜にしばしばみられる水素脆化の問題を生じさせ
ない。According to the present invention, a Pd thin film or Pd is formed in the pores.
Provided is a method for producing a hydrogen separation membrane made of a porous ceramics membrane on which a hydrogen selective permeable membrane made of an alloy thin film is formed. Here formed inside the pores of the porous ceramic film
The Pd thin film or Pd alloy thin film has no pinhole, is excellent in hydrogen selective permeability and hydrogen permeation rate, and does not cause the problem of hydrogen embrittlement often found in hydrogen separation membranes.
【００１６】[0016]
【実施例】次に、実施例について本発明を説明する。EXAMPLES The present invention will now be described with reference to examples.
【００１７】実施例１
多孔質セラミックス膜として多孔質α-アルミナ中空糸
膜(外径2.6mm、内径2.0mm、平均細孔径150nm、平均細孔
率40%)を、またPd膜源物質として酢酸パラジウム20mgを
それぞれ用い、長さ250mm、内径28mmのパイレックス管
を反応器とする図１に示される装置を用い、CVD法を行
った。Example 1 A porous α-alumina hollow fiber membrane (outer diameter 2.6 mm, inner diameter 2.0 mm, average pore diameter 150 nm, average pore ratio 40%) was used as the porous ceramic membrane, and acetic acid was used as the Pd membrane source material. A CVD method was carried out using 20 mg of palladium and a Pyrex tube having a length of 250 mm and an inner diameter of 28 mm as a reactor as shown in FIG.
【００１８】まず、反応器をロータリポンプで排気しな
がら、6ml/分(STP)の供給量のアルゴンガスを流し、多
孔質α-アルミナ中空糸膜内をロータリポンプで、0.2〜
0.3ml/分(STP)の排気量で排気することにより、反応器
内を約150〜200Paの圧力に、また多孔質α-アルミナ中
空糸膜内を約6〜9Paの圧力にそれぞれ制御する。First, while evacuating the reactor with a rotary pump, an argon gas having a supply rate of 6 ml / min (STP) was caused to flow, and the inside of the porous α-alumina hollow fiber membrane was moved by a rotary pump to 0.2-
By evacuating with a displacement of 0.3 ml / min (STP), the pressure inside the reactor is controlled to about 150 to 200 Pa, and the inside of the porous α-alumina hollow fiber membrane is controlled to about 6 to 9 Pa.
【００１９】そして、昇温速度13℃/分で400℃迄昇温さ
せ、酢酸パラジウムを熱分解させて2時間の製膜を行っ
たところ、ピンホールのない緻密なPd薄膜が中空糸膜外
表面の細孔内に形成された。ピンホールの有無は、透過
部温度300℃で水素透過速度の圧力依存性を調べ、図２
のグラフに示したように、水素透過速度が膜両側の水素
分圧差によらず一定であることから、ピンホールフリー
であると判断された。Then, the temperature was raised to 400 ° C. at a heating rate of 13 ° C./min, and palladium acetate was thermally decomposed to form a film for 2 hours. As a result, a dense Pd thin film without pinholes was found to be outside the hollow fiber film. It was formed in the surface pores. For the presence or absence of pinholes, the pressure dependence of the hydrogen permeation rate was examined at a permeation temperature of 300 ° C,
As shown in the graph, the hydrogen permeation rate was constant irrespective of the hydrogen partial pressure difference on both sides of the membrane, so that it was judged to be pinhole-free.
【００２０】また、このPd薄膜形成中空糸膜の透過性能
を、種々温度を変えて水素ガス透過係数として測定する
と、図３のグラフに示されるような結果が得られた。When the permeation performance of this Pd thin film-formed hollow fiber membrane was measured as a hydrogen gas permeation coefficient at various temperatures, the results shown in the graph of FIG. 3 were obtained.
【００２１】更に、Pd系薄膜は、水素透過に伴う水素の
吸収と吐き出しとがくり返される過程で脆化すること前
述の如くであるので、100℃⇔300℃の昇・降温をくり返
して水素透過速度を測定したが、図４のグラフに示され
るように、水素脆化の問題は生じていなかった。Further, the Pd-based thin film becomes brittle during the process of repeated absorption and discharge of hydrogen accompanying hydrogen permeation. As described above, the temperature rise and fall between 100 ° C and 300 ° C is repeated. The permeation rate was measured, but as shown in the graph of FIG. 4, the problem of hydrogen embrittlement did not occur.
【００２２】実施例２
実施例１において、製膜温度を500℃、昇温速度を17℃/
分に変更して製膜したところ、ピンホールのない緻密な
Pd薄膜が、中空糸膜外表面側の細孔内に形成された。Example 2 In Example 1, the film forming temperature was 500 ° C. and the temperature rising rate was 17 ° C. /
The film was formed after changing to minutes,
A Pd thin film was formed in the pores on the outer surface side of the hollow fiber membrane.
【００２３】このPd薄膜形成中空糸膜の水素ガス透過係
数の透過温度依存性は、図５のグラフに示される。この
場合の水素ガス透過係数は、製膜温度400℃の場合より
も低下していた。The graph of FIG. 5 shows the permeation temperature dependence of the hydrogen gas permeation coefficient of this Pd thin film forming hollow fiber membrane. The hydrogen gas permeability coefficient in this case was lower than that at the film forming temperature of 400 ° C.
【００２４】実施例３
実施例１において、製膜温度を300℃、昇温速度を10℃/
分に変更して製膜したところ、ピンホールのない緻密な
Pd薄膜が、中空糸膜外表面の細孔内に形成された。Example 3 In Example 1, the film forming temperature was 300 ° C. and the temperature rising rate was 10 ° C. /
The film was formed after changing to minutes,
A Pd thin film was formed in the pores on the outer surface of the hollow fiber membrane.
【００２５】このPd薄膜形成中空糸膜の水素ガス透過係
数の透過温度依存性は、図６のグラフに示される。この
場合の水素ガス透過係数は、製膜温度400℃の場合より
も大きくなっていた。The graph of FIG. 6 shows the permeation temperature dependence of the hydrogen gas permeation coefficient of this Pd thin film-formed hollow fiber membrane. The hydrogen gas permeation coefficient in this case was larger than that at the film forming temperature of 400 ° C.
【００２６】また、得られたPd薄膜形成多孔質α-アル
ミナ中空糸膜のPd薄膜の膜表面SEM写真から、多孔質α-
アルミナ中空糸膜の外表面の細孔が、Pdによって隙間な
く埋められていることが確認された(図８〜10および図1
1〜12参照)。更に、Pd薄膜の膜断面のSEM-EDX分析結果
から、Pdは多孔質α-アルミナ中空糸膜の表面細孔内に
確実に入っていることも確認された(図13〜15参照)。Further, from the obtained SEM photograph of the Pd thin film of the obtained Pd thin film-forming porous α-alumina hollow fiber membrane, the porous α-
It was confirmed that the pores on the outer surface of the alumina hollow fiber membrane were completely filled with Pd (Figs. 8 to 10 and Fig. 1).
(See 1-12). Furthermore, it was also confirmed from the SEM-EDX analysis result of the membrane cross section of the Pd thin film that Pd was surely contained in the surface pores of the porous α-alumina hollow fiber membrane (see FIGS. 13 to 15).
【００２７】実施例４
実施例３において、多孔質α-アルミナ中空糸膜の外表
面側に、ゾル・ゲル法によるγ-アルミナ薄膜(平均膜厚
5μm、平均細孔径5nm)を形成させたものを用いて製膜し
たところ、ピンホールのない緻密なPd薄膜が、中空糸膜
外表面側の細孔内に形成された。Example 4 In Example 3, on the outer surface side of the porous α-alumina hollow fiber membrane, a γ-alumina thin film (average film thickness) obtained by the sol-gel method was used.
When a film having a thickness of 5 μm and an average pore diameter of 5 nm) was formed, a dense Pd thin film without pinholes was formed in the pores on the outer surface side of the hollow fiber membrane.
【００２８】このPd薄膜形成中空糸膜の水素ガス透過係
数の透過温度依存性は、図７のグラフに示される。ここ
で、２種類の○で示されたものは、それぞれ水素ガスの
透過係数を示しており、また２種類の△で示されたもの
は、それぞれ窒素ガスの透過係数を示している。The graph of FIG. 7 shows the permeation temperature dependence of the hydrogen gas permeation coefficient of this Pd thin film-formed hollow fiber membrane. Here, the two kinds of circles indicate the permeability coefficient of hydrogen gas, and the two kinds of triangles indicate the permeability coefficient of nitrogen gas, respectively.
【００２９】なお、ガス透過試験は、中空糸膜の中央部
(長さ約10mm)以外の部分をすべて封着ガラスで封止し、
この中央部の外側に水素ガスまたは窒素ガスを流通させ
た後、Pd薄膜を透過したガス成分をアルゴンガスに同伴
させて、TCD-ガスクロマトグラフィーで分析することに
より行われた。The gas permeation test was conducted at the center of the hollow fiber membrane.
Seal all parts except (about 10 mm in length) with sealing glass,
After hydrogen gas or nitrogen gas was circulated to the outside of this central portion, the gas component that permeated the Pd thin film was made to accompany with argon gas and analyzed by TCD-gas chromatography.
【図１】本発明方法に用いられるCVD装置の概要図であ
る。FIG. 1 is a schematic diagram of a CVD apparatus used in the method of the present invention.
【図２】実施例１で得られた水素分離膜の水素ガス透過
係数の膜両面水素分圧差依存性を示すグラフである。FIG. 2 is a graph showing the hydrogen gas permeability coefficient dependence of the hydrogen gas permeation coefficient of the hydrogen separation membrane obtained in Example 1 on both sides of the membrane.
【図３】実施例１で得られた水素分離膜の水素ガス透過
係数の透過温度依存性を示すグラフである。FIG. 3 is a graph showing the permeation temperature dependence of the hydrogen gas permeation coefficient of the hydrogen separation membrane obtained in Example 1.
【図４】実施例１で得られた水素分離膜の水素脆化特性
を示すグラフである。FIG. 4 is a graph showing hydrogen embrittlement characteristics of the hydrogen separation membrane obtained in Example 1.
【図５】実施例２で得られた水素分離膜の水素ガス透過
係数の透過温度依存性を示すグラフである。5 is a graph showing the permeation temperature dependence of the hydrogen gas permeation coefficient of the hydrogen separation membrane obtained in Example 2. FIG.
【図６】実施例３で得られた水素分離膜の水素ガス透過
係数の透過温度依存性を示すグラフである。FIG. 6 is a graph showing the permeation temperature dependence of the hydrogen gas permeation coefficient of the hydrogen separation membrane obtained in Example 3.
【図７】実施例４で得られた水素分離膜の水素ガス透過
係数の透過温度依存性を示すグラフである。FIG. 7 is a graph showing the permeation temperature dependence of the hydrogen gas permeation coefficient of the hydrogen separation membrane obtained in Example 4.
【図８】実施例３で得られたPd薄膜形成多孔質α-アル
ミナ中空糸膜のPd薄膜の膜表面SEM写真である。FIG. 8 is a film surface SEM photograph of the Pd thin film of the Pd thin film-forming porous α-alumina hollow fiber membrane obtained in Example 3.
【図９】実施例３で得られたPd薄膜形成多孔質α-アル
ミナ中空糸膜のPd薄膜の膜断面SEM写真である。9 is a film cross-sectional SEM photograph of the Pd thin film of the Pd thin film-forming porous α-alumina hollow fiber membrane obtained in Example 3. FIG.
【図10】実施例３で得られたPd薄膜形成多孔質α-アル
ミナ中空糸膜のPd薄膜面SEM写真である。FIG. 10 is a SEM photograph of the Pd thin film surface of the Pd thin film-forming porous α-alumina hollow fiber membrane obtained in Example 3.
【図11】実施例３で用いられた多孔質α-アルミナ中空
糸膜の膜表面SEM写真である。FIG. 11 is a SEM photograph of the surface of the porous α-alumina hollow fiber membrane used in Example 3.
【図12】実施例３で用いられた多孔質α-アルミナ中空
糸膜の膜断面SEM写真である。FIG. 12 is a SEM photograph of a cross section of a porous α-alumina hollow fiber membrane used in Example 3.
【図13】実施例３で得られたPd薄膜形成多孔質α-アル
ミナ中空糸膜のPd薄膜の断面二次電子像写真である。FIG. 13 is a cross-sectional secondary electron image photograph of the Pd thin film of the Pd thin film-forming porous α-alumina hollow fiber membrane obtained in Example 3.
【図14】実施例３で得られたPd薄膜形成多孔質α-アル
ミナ中空糸膜のPd薄膜のPd線分析プロファイル写真であ
る。FIG. 14 is a Pd line analysis profile photograph of the Pd thin film of the Pd thin film-forming porous α-alumina hollow fiber membrane obtained in Example 3.
【図15】実施例３で得られたPd薄膜形成多孔質α-アル
ミナ中空糸膜のPd薄膜のAl線分析プロファイル写真であ
る。FIG. 15 is an Al line analysis profile photograph of the Pd thin film of the Pd thin film-forming porous α-alumina hollow fiber membrane obtained in Example 3.
１ 反応器 ３ 多孔質セラミックス中空糸膜 ６，７ ロータリポンプ １０ アルゴンガス導入管 １２ 電気炉 １４ Pd膜源物質 1 reactor 3 Porous ceramic hollow fiber membrane 6,7 Rotary pump 10 Argon gas introduction tube 12 Electric furnace 14 Pd Membrane source material
───────────────────────────────────────────────────── フロントページの続き (72)発明者 諸岡 成治 福岡県福岡市東区美和台３−29−２ (72)発明者 草壁 克己 福岡県福岡市東区箱崎６−10−１ 九州 大学工学部内 (72)発明者 前田 英明 福岡県福岡市東区箱崎６−10−１ 九州 大学工学部内 (56)参考文献 特開 昭62−121616（ＪＰ，Ａ) 特開 平４−349926（ＪＰ，Ａ) 特開 昭50−55965（ＪＰ，Ａ) 特開 平６−277472（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01D 67/00 - 71/82 510 B01D 53/22 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Seiji Morooka 3-29-2 Miwadai, Higashi-ku, Fukuoka-shi, Fukuoka (72) Katsumi Kusakabe 6-10-1 Hakozaki, Higashi-ku, Fukuoka-shi, Fukuoka Kyushu University Faculty of Engineering ( 72) Inventor Hideaki Maeda 6-10-1, Hakozaki, Higashi-ku, Fukuoka, Fukuoka Prefecture Faculty of Engineering, Kyushu University (56) References JP-A-62-121616 (JP, A) JP-A-4-349926 (JP, A) JP 50-55965 (JP, A) JP-A-6-277472 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) B01D 67/00-71/82 510 B01D 53/22
Claims (2)
設け、気化させたPd膜源またはPd合金膜源を多孔質セラ
ミックス膜の細孔内に吸引しながら、細孔内でPd膜化ま
たはPd合金膜化させることを特徴とする水素分離膜の製
造法。 1. A pressure difference is applied to both sides of a porous ceramic membrane.
The Pd film source or Pd alloy film source that has been vaporized is installed in the porous ceramic.
While sucking into the pores of the mix membrane, Pd film is formed inside the pores.
Or a Pd alloy membrane is used to produce a hydrogen separation membrane.
Construction method.
-アルミナ膜またはその表面にゾル・ゲル法によるγ-ア
ルミナ薄膜を形成させたものが用いられる請求項１記載
の水素分離膜の製造法。2. The porous ceramic film as a porous α
2. The method for producing a hydrogen separation membrane according to claim 1 , wherein an alumina membrane or a surface of which a γ-alumina thin film is formed by a sol-gel method is used.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25500493A JP3373006B2 (en) | 1993-09-17 | 1993-09-17 | Manufacturing method of hydrogen separation membrane |
Publications (2)
| Publication Number | Publication Date |
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| JPH07136477A JPH07136477A (en) | 1995-05-30 |
| JP3373006B2 true JP3373006B2 (en) | 2003-02-04 |
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ID=17272868
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Cited By (1)
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|---|---|---|---|---|
| WO2008102509A1 (en) | 2007-02-19 | 2008-08-28 | Mitsubishi Gas Chemical Company, Inc. | Hydrogen purification method, hydrogen separation membrane, and hydrogen purification apparatus |
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| JP5294229B2 (en) * | 2007-02-16 | 2013-09-18 | 独立行政法人産業技術総合研究所 | Hydrogen permeable membrane manufacturing equipment using chemical vapor deposition |
| JP6089814B2 (en) * | 2013-03-12 | 2017-03-08 | 東京瓦斯株式会社 | Hydrogen separation method |
| JP6384831B2 (en) * | 2014-09-19 | 2018-09-05 | 東京瓦斯株式会社 | Hydrogen separator and hydrogen separation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008102509A1 (en) | 2007-02-19 | 2008-08-28 | Mitsubishi Gas Chemical Company, Inc. | Hydrogen purification method, hydrogen separation membrane, and hydrogen purification apparatus |
| JP5229503B2 (en) * | 2007-02-19 | 2013-07-03 | 三菱瓦斯化学株式会社 | Hydrogen purification method, hydrogen separation membrane, and hydrogen purification apparatus |
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