JPH0553527B2 - - Google Patents
Info
- Publication number
- JPH0553527B2 JPH0553527B2 JP62160382A JP16038287A JPH0553527B2 JP H0553527 B2 JPH0553527 B2 JP H0553527B2 JP 62160382 A JP62160382 A JP 62160382A JP 16038287 A JP16038287 A JP 16038287A JP H0553527 B2 JPH0553527 B2 JP H0553527B2
- Authority
- JP
- Japan
- Prior art keywords
- palladium
- plating
- bath
- electrolytic
- membrane
- 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
Links
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 67
- 229910052763 palladium Inorganic materials 0.000 claims description 32
- 238000007747 plating Methods 0.000 claims description 16
- 239000000919 ceramic Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 239000010409 thin film Substances 0.000 claims description 10
- 229910001252 Pd alloy Inorganic materials 0.000 claims description 8
- 239000010408 film Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000012528 membrane Substances 0.000 description 20
- 239000007789 gas Substances 0.000 description 19
- 238000009713 electroplating Methods 0.000 description 12
- 238000007772 electroless plating Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 4
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- -1 palladium ions Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- HVTHJRMZXBWFNE-UHFFFAOYSA-J sodium zincate Chemical compound [OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Zn+2] HVTHJRMZXBWFNE-UHFFFAOYSA-J 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- 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
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/04—Purification or separation of nitrogen
- C01B21/0405—Purification or separation processes
- C01B21/0433—Physical processing only
- C01B21/0438—Physical processing only by making use of membranes
- C01B21/0444—Physical processing only by making use of membranes characterised by the membrane
-
- 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
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、ガス分離用パラジウム又はパラジウ
ム合金薄膜の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing a palladium or palladium alloy thin film for gas separation.
（従来の技術及びその問題点）
従来、ガス、特に水素のみを透過させる金属の
一つとして、パラジウム及びその合金は知られて
いる。それをガス分離膜として使用する場合、圧
延・成型などを行う必要があるが、特に中空状に
加工する場合には、展延性に欠けるため加工性に
問題が生じ、100μｍ以下の薄膜を得ることは困
難であつた。したがつて、もしそれ以外のより薄
い膜を製造する技術が完成されれば、膜厚が小さ
くなることで透過速度をそれに反比例して大きく
することができる。加えて、パラジウムなどの貴
金属類は高価であり、より薄い膜を製造する技術
が確立されることにより、膜自体の価格をも大幅
に下げることができるであろう。(Prior Art and its Problems) Palladium and its alloys have been known as metals that allow only gas, especially hydrogen, to pass therethrough. When using it as a gas separation membrane, it is necessary to perform rolling, molding, etc., but especially when processing it into a hollow shape, there is a problem with workability due to the lack of malleability, and it is difficult to obtain a thin film of 100 μm or less. was difficult. Therefore, if the technology to manufacture other thinner membranes is perfected, the permeation rate can be inversely increased by reducing the membrane thickness. In addition, noble metals such as palladium are expensive, and the establishment of technology for manufacturing thinner membranes could significantly reduce the price of the membrane itself.
ところで従来の水素透過膜の製造方法として通
気性多孔質金属板の細孔を金属パラジウムで閉塞
し、その金属パラジウムの表面にパラジウム黒等
を付着させる方法があるが（特開昭51−131473
号）、孔の径が大きいセラミツク多孔質には適用
できず、また基板全体を所定の厚さで完全に被覆
する緻密な被膜を形成することはできなかつた。 By the way, as a conventional method for manufacturing a hydrogen permeable membrane, there is a method in which the pores of an air-permeable porous metal plate are closed with metal palladium, and palladium black or the like is deposited on the surface of the metal palladium (Japanese Patent Laid-Open No. 51-131473).
No. 1) cannot be applied to ceramic porous materials with large pore diameters, and it is also not possible to form a dense film that completely covers the entire substrate with a predetermined thickness.
したがつて、本発明の目的は、多孔質セラミツ
ク材の表面に所定の厚さで、パラジウム又はパラ
ジウム合金の緻密な被膜を形成することができる
ガス分離薄膜の製造方法を提供することにある。 Therefore, an object of the present invention is to provide a method for producing a gas separation thin film that can form a dense coating of palladium or palladium alloy on the surface of a porous ceramic material with a predetermined thickness.
（問題点を解決するための手段）
本発明者らは、以上のような観点から、より薄
いパラジウム膜を形成させる方法について、鋭意
研究を重ねた結果、支持体としてセラミツクスを
用い、その表面上に無電解めつき及び電解めつき
法の組合せによつてパラジウム又はパラジウム合
金を薄膜として形成させる方法が、極めて有効で
あることを見出し、本発明をなすに至つた。(Means for Solving the Problems) From the above-mentioned viewpoint, the present inventors have conducted intensive research into a method for forming a thinner palladium film. The inventors have discovered that a method of forming palladium or a palladium alloy as a thin film by a combination of electroless plating and electrolytic plating is extremely effective, leading to the present invention.
すなわち本発明は、多孔質セラミツク層の表面
に無電解パラジウムめつきを施して電気伝導性を
付与した後、その上に電解パラジウムめつきによ
り、表面を完全に被覆する電解パラジウム又はパ
ラジウム合金めつき膜の被覆を形成することを特
徴とするガス分離薄膜の製造方法を提供するもの
である。 That is, the present invention provides electrolytic palladium or palladium alloy plating, in which electroless palladium plating is applied to the surface of a porous ceramic layer to impart electrical conductivity, and then electrolytic palladium is applied thereon to completely cover the surface. The present invention provides a method for producing a gas separation thin film, which comprises forming a membrane coating.
本発明方法により得られるガス分離膜の１例を
断面模式図として第１図に示した。 An example of a gas separation membrane obtained by the method of the present invention is shown in FIG. 1 as a schematic cross-sectional view.
図中１は多孔質セラミツクス層、２は該セラミ
ツクス層のセラミツク粒子であり、３は無電解め
つき層、４はその上に形成した電解めつき層であ
る。なお、矢印は通常の、ガスの流れ方向であ
り、この逆方向でもよい。 In the figure, 1 is a porous ceramic layer, 2 is ceramic particles of the ceramic layer, 3 is an electroless plating layer, and 4 is an electrolytic plating layer formed thereon. Note that the arrow indicates the normal gas flow direction, and the opposite direction may be used.
無電解めつき層３の厚さは通常、１〜3μｍ、
電解めつき層４は通常、厚さ10〜30μｍでよい。
また支持体としての多孔質セラミツクス層の厚さ
には、特に制限はなく、使用条件に機械的に耐え
得るものであればよい。また多孔質セラミツクス
の孔径は1μｍ程度以下であればよい。 The thickness of the electroless plating layer 3 is usually 1 to 3 μm,
The electroplated layer 4 usually has a thickness of 10 to 30 μm.
Further, there is no particular restriction on the thickness of the porous ceramic layer as a support, as long as it can mechanically withstand the conditions of use. Further, the pore diameter of the porous ceramics may be about 1 μm or less.
本発明方法において、まず本来は電気不導体で
あるセラミツクス上に無電解パラジウムめつきを
施すことで、電気伝導性を付与する。次いで電解
パラジウムめつきを行うことで、全体としては第
１図に示したような構造となり、ガス分離膜とし
て使用に耐え得る緻密な薄膜を作ることができ
る。 In the method of the present invention, electroless palladium plating is first applied to ceramics, which are originally electrically nonconducting, to impart electrical conductivity. Next, by performing electrolytic palladium plating, the structure as a whole becomes as shown in FIG. 1, and a dense thin film that can be used as a gas separation membrane can be produced.
本発明方法において用いられる無電解パラジウ
ムめつきとは、化学的酸化還元反応を利用するも
ので、２価のパラジウムイオン（Pd2+）を還元
剤を用いて、被めつき物上に金属パラジウム
（Pd）として還元析出させるものである。無電解
めつき浴としては、次亜リン酸ナトリウム浴、ヒ
ドラジン浴などを用いることができる。 The electroless palladium plating used in the method of the present invention utilizes a chemical redox reaction, and uses divalent palladium ions (Pd 2+ ) as a reducing agent to deposit metallic palladium onto the object to be plated. (Pd) is reduced and precipitated. As the electroless plating bath, a sodium hypophosphite bath, a hydrazine bath, etc. can be used.
この無電解めつきは、下地めつきとしてセラミ
ツクス支持体に電気伝導性を付与し、また、多孔
質セラミツクスの孔を適度に封鎖する点で重要で
ある。 This electroless plating is important in that it imparts electrical conductivity to the ceramic support as a base plating and also appropriately closes the pores of the porous ceramic.
次いで電解パラジウムめつきとは、２価のパラ
ジウムイオンを電解浴中で、その陰極上に電気的
還元を行つて析出させることで行うことができ
る。電解めつき浴としてはジアミノ亜硝酸パラジ
ウム浴、テトラミンジクロロパラジウム浴及び市
販のパラジウム浴、例えばパラデツクス91（商品
名）、パラデツクスMS（商品名）を用いることが
できる。 Next, electrolytic palladium plating can be performed by electrically reducing and depositing divalent palladium ions on the cathode in an electrolytic bath. As the electrolytic plating bath, diaminonitrite palladium bath, tetramine dichloropalladium bath and commercially available palladium baths such as Paradex 91 (trade name) and Paradex MS (trade name) can be used.
この電解パラジウムめつきにより、無電解めつ
き層の上にパラジウム又はパラジウム合金の薄膜
を形成する。この場合電解めつき層の厚さは上述
の範囲が好ましいが、めつき時間・電圧・電流な
どを制御することにより、めつき厚を調整するこ
とができる。通常、めつき時間は30〜90分、浴PH
６〜10、電流密度0.5〜3A／ｄm2、温度40〜90℃
とするのが好ましい。その他のめつき条件は通常
の電解めつき法に準じて設定できる。 This electrolytic palladium plating forms a thin film of palladium or palladium alloy on the electroless plating layer. In this case, the thickness of the electrolytically plated layer is preferably within the above range, but the plating thickness can be adjusted by controlling the plating time, voltage, current, etc. Normally, plating time is 30 to 90 minutes, bath pH
6-10, current density 0.5-3A/ dm2 , temperature 40-90℃
It is preferable that Other plating conditions can be set according to normal electrolytic plating methods.
本発明に用いられる多孔質セラミツクスの形状
は特に制限はなく、板状、管状などが好ましく用
いられる。 The shape of the porous ceramic used in the present invention is not particularly limited, and plate-like, tubular, etc. shapes are preferably used.
（発明の効果）
本発明は、比較的大きな孔径を有する支持体を
用いても、より緻密なパラジウム又はパラジウム
合金薄膜が得られるという点に、１つの特徴を有
している。これにより、支持体部での圧力損失は
無視し得ることになるから、ガスの分離のための
操作圧を軽減することが可能になる。特に本発明
方法により得られるガス分離薄膜は水素の選択透
過性の優れるものである。また本発明方法によれ
ば100μｍ以下の薄膜からなるガス分離膜を形成
することができる。(Effects of the Invention) One feature of the present invention is that a denser palladium or palladium alloy thin film can be obtained even when a support having a relatively large pore size is used. This makes it possible to ignore the pressure loss in the support section, making it possible to reduce the operating pressure for gas separation. In particular, the gas separation membrane obtained by the method of the present invention has excellent hydrogen permselectivity. Further, according to the method of the present invention, a gas separation membrane consisting of a thin film of 100 μm or less can be formed.
（実施例）
次に実施例に基づき本発明をさらに詳細に説明
する。(Example) Next, the present invention will be described in more detail based on Examples.
実施例
(1) 無電解めつき
表１に示したような組成の無電解めつき浴
（PH10.4〜11.0）を調整し、その浴温度は35〜
45℃の範囲内になるように制御する。Example (1) Electroless plating An electroless plating bath (PH10.4-11.0) having the composition shown in Table 1 was prepared, and the bath temperature was 35-11.0.
Control to within 45℃.
表１ 無電解めつき浴の組成・操作条件
次亜リン酸ナトリウム ８〜12ｇ／
塩化パラジウム 1.8〜2.2ｇ／
塩化アンモニウム 24〜30ｇ／
アンモニア水（28％） 280〜350ml／
塩酸（38％） 3.2〜4.8ml／
温 度 35〜45℃
PH 10.4〜11.0
時 間 50〜70分
浴中へ、脱脂処理及び活性化処理を施した多
孔質セラミツクス板あるいは管（孔径1μｍ、
セラミツクス厚１mm）を浸し、50〜70分間放置
する。その際の、液量（cm3）と被めつき物面積
（cm2）との比は、８〜10とした。こうして出来
上がつた無電解めつき被覆物を、洗浄及び封孔
処理のため、沸騰水中に15分間浸漬した。Table 1 Composition and operating conditions of electroless plating bath Sodium hypophosphite 8-12g / Palladium chloride 1.8-2.2g / Ammonium chloride 24-30g / Aqueous ammonia (28%) 280-350ml / Hydrochloric acid (38%) 3.2 ~4.8ml/Temperature: 35~45℃ PH: 10.4~11.0 Time: 50~70 minutes Into the bath, add a porous ceramic plate or tube (pore size: 1μm,
Soak ceramics (1 mm thick) and leave for 50 to 70 minutes. At that time, the ratio of the liquid amount (cm 3 ) to the area of the covered object (cm 2 ) was set to 8 to 10. The electroless plated coating thus completed was immersed in boiling water for 15 minutes for cleaning and sealing.
こうして得られた被覆物（厚さ2.6μｍ）の電
気抵抗は0.03Ω／cm程度であり、以下で行う電
解めつきに必要な電気伝導性が付与されたこと
が確認された。 The electrical resistance of the thus obtained coating (thickness: 2.6 μm) was approximately 0.03 Ω/cm, and it was confirmed that the electrical conductivity required for the electrolytic plating performed below was provided.
(2) 電解めつき
電解めつき浴としては、次の３種類を用い
た。(2) Electrolytic plating The following three types of electrolytic plating baths were used.
(イ) ジアミノ亜硝酸パラジウム浴
(ロ) テトラミンジクロロパラジウム浴
(ハ) パラデツクス浴（商品名、日本エレクトロ
プレテイングエンジニヤーズ社製）
(イ)、(ロ)は、パラジウム膜を得るための浴であ
り、最適組成・操作条件を表２、表３にそれぞ
れ示した。また、(ハ)は、パラジウム合金（組
成：Pd90〜95％、Ni5〜10％）膜を得るための
浴であり、操作条件についてのみ表４に示し
た。(a) Diaminonitrite palladium bath (b) Tetramine dichloropalladium bath (c) Paradex bath (trade name, manufactured by Nippon Electroplating Engineers) (a) and (b) are baths for obtaining a palladium film. The optimum composition and operating conditions are shown in Tables 2 and 3, respectively. Further, (c) is a bath for obtaining a palladium alloy (composition: Pd 90-95%, Ni 5-10%) film, and only the operating conditions are shown in Table 4.
表２ ジアミノ亜硝酸浴の組成・操作条件
亜鉛酸ナトリウム ８〜12ｇ／
硝酸アンモニウム 80〜120ｇ／
ジアミノ亜硝酸パラジウム 20〜24ｇ／
アンモニア水（28％） 40〜60ml／
PH 9.3〜9.7
温 度 50〜70℃
時 間 50〜70分
電流密度 1.8〜2.2A／ｄm2
表３
テトラミジクロロパラジウム浴の組成・操作
条件
硝酸アンモニウム 80〜120ｇ／
亜硝酸ナトリウム ４〜６ｇ／
リン酸水素第２アンモニウム ８〜12ｇ／
テトラミンジクロロパラジウム 20〜30ｇ／
PH 9.3〜9.7
温 度 75〜85℃
時 間 60分
電流密度 0.8〜1.2A／ｄm2
表４ パラデツクス91操作条件
PH 6.5〜7.5
温 度 50〜60℃
時 間 60分
電流密度 1.8〜2.2A／ｄm2
各電解めつきは、いずれも陽極として白金を
用い、表２〜表４の組成及び条件に調整した
後、定電流法によつて行つた。操作終了後、洗
浄及び封孔処理のため、沸騰水中に15分間浸漬
し、その後乾燥器中で120℃にて乾燥した。こ
のようにして(イ)、(ロ)、(ハ)の電解めつき浴から得
られた電解めつき試料をそれぞれ試料(イ)、(ロ)、
(ハ)とした。それぞれの電解めつき層の厚さは
20μｍ、15μｍ、20μｍであつた。Table 2 Composition and operating conditions of diaminonitrite bath Sodium zincate 8-12g / Ammonium nitrate 80-120g / Palladium diaminonitrite 20-24g / Ammonia water (28%) 40-60ml / PH 9.3-9.7 Temperature 50-70 °C Time 50 to 70 minutes Current density 1.8 to 2.2 A/dm 2 Table 3 Composition and operating conditions of tetramidichloropalladium bath Ammonium nitrate 80 to 120 g/ Sodium nitrite 4 to 6 g/ Second ammonium hydrogen phosphate 8 to 12 g/ Tetramine dichloropalladium 20-30g/PH 9.3-9.7 Temperature 75-85℃ Time 60 minutes Current density 0.8-1.2A/dm 2 Table 4 Paradex 91 operating conditions PH 6.5-7.5 Temperature 50-60℃ Time 60 minutes Current density: 1.8 to 2.2 A/dm 2 In each electrolytic plating, platinum was used as an anode, and after adjusting the composition and conditions as shown in Tables 2 to 4, the electrolytic plating was carried out by a constant current method. After the operation was completed, it was immersed in boiling water for 15 minutes for cleaning and sealing, and then dried in a dryer at 120°C. In this way, the electrolytic plating samples obtained from the electrolytic plating baths of (a), (b), and (c) are used as samples (a), (b), and (c), respectively.
(c). The thickness of each electroplated layer is
They were 20 μm, 15 μm, and 20 μm.
(3) 各種ガスのめつき膜中の透過速度測定
上記のようにして得られためつき膜中のアル
ゴン、ヘリウム及び水素ガス透過速度を180℃
で測定した結果を以下に示す。(3) Measuring the permeation rate of various gases in the plated membrane The permeation rate of argon, helium, and hydrogen gas in the plated membrane obtained as above was measured at 180°C.
The results measured are shown below.
まず(イ)のジアミノ亜硝酸パラジウム浴及び(ロ)
のテトラミジクロロパラジウム浴を用いて作成
したパラジウム膜についての結果を第２図及び
第３図に示した。縦軸は各ガスの透過係数Pp
（mol／m.s.Pa）、横軸は各ガスの分子量Ｍ
（ｇ／mol）の平方根の逆数（１／√）で表
わしたものである。両図から明らかなように、
アルゴン、ヘリウムガスについては、Ppが
１／√に比例している（クヌーセンの法則）
ということから、めつき膜中に微細孔が若干残
存していることを意味している。したがつて、
その微細孔を通り抜ける水素の量は、外挿によ
り第２図、第３図中のＡ点に相当することにな
る。その残りの部分がパラジウム金属中を拡散
透過することになる。一方、通常の微細孔の多
孔質膜による水素分離のアルゴンガスに対する
選択性は、透過係数比で、4.47である。これに
対して、ジアミノ亜硝酸パラジウム浴使用によ
り作成した膜のそれは11.0、テトラミンジクロ
ロパラジウム浴使用により作成した膜のそれは
12.6と、それぞれ2.5倍、2.8倍大きい性能を有
することがわかる。 First, (a) diaminonitrite palladium bath and (b)
The results for palladium membranes prepared using the tetramidichloropalladium bath are shown in FIGS. 2 and 3. The vertical axis is the permeability coefficient Pp of each gas
(mol/msPa), the horizontal axis is the molecular weight M of each gas
It is expressed as the reciprocal (1/√) of the square root of (g/mol). As is clear from both figures,
For argon and helium gas, Pp is proportional to 1/√ (Knudsen's law)
This means that some micropores remain in the plating film. Therefore,
By extrapolation, the amount of hydrogen passing through the micropores corresponds to point A in FIGS. 2 and 3. The remaining portion will diffuse through the palladium metal. On the other hand, the selectivity for hydrogen separation with respect to argon gas using a normal porous membrane with micropores is 4.47 in terms of permeability coefficient ratio. On the other hand, the value of the membrane prepared using diaminonitrite palladium bath is 11.0, and that of the membrane prepared using tetramine dichloropalladium bath is 11.0.
12.6, which is 2.5 times and 2.8 times higher in performance, respectively.
次に(ハ)のパラデツクス浴を用いて作成したパ
ラジウム−ニツケルめつき膜についての結果を
第４図に示す。アルゴン、ヘリウムガスについ
ては、透過係数はゼロ、すなわち透過が認めら
れなかつた。この場合は、水素ガスのみを透過
させる膜が得られたことがわかる。 Next, FIG. 4 shows the results for a palladium-nickel plated film prepared using the paradox bath (c). For argon and helium gas, the permeation coefficient was zero, that is, no permeation was observed. In this case, it can be seen that a membrane that allows only hydrogen gas to pass through was obtained.
第１図は本発明方法により得られためつき膜の
断面模式図、第２図、第３図及び第４図は実施例
で得られたガス分離薄膜の各種ガスに対する透過
係数を示すグラフである。
FIG. 1 is a schematic cross-sectional view of a tamped membrane obtained by the method of the present invention, and FIGS. 2, 3, and 4 are graphs showing the permeability coefficients for various gases of the gas separation thin membranes obtained in Examples. .
Claims (1)
ウムめつきを施して電気伝導性を付与した後、そ
の上に、電解パラジウムめつきにより、表面を完
全に被覆する電解パラジウム又はパラジウム合金
めつき膜の被膜を形成することを特徴とするガス
分離薄膜の製造方法。1. Electroless palladium plating is applied to the surface of the porous ceramic layer to impart electrical conductivity, and then an electrolytic palladium or palladium alloy plating film is applied thereon to completely cover the surface by electrolytic palladium plating. A method for producing a gas separation thin film, the method comprising forming a film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16038287A JPS644216A (en) | 1987-06-26 | 1987-06-26 | Production of thin membrane for separating gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16038287A JPS644216A (en) | 1987-06-26 | 1987-06-26 | Production of thin membrane for separating gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS644216A JPS644216A (en) | 1989-01-09 |
| JPH0553527B2 true JPH0553527B2 (en) | 1993-08-10 |
Family
ID=15713756
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16038287A Granted JPS644216A (en) | 1987-06-26 | 1987-06-26 | Production of thin membrane for separating gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS644216A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004057993A (en) * | 2002-07-31 | 2004-02-26 | Dainippon Printing Co Ltd | Method of manufacturing hydrogen producing filter |
| WO2014126027A1 (en) | 2013-02-12 | 2014-08-21 | サンデン株式会社 | Showcase cooling device |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2048849A1 (en) * | 1990-08-10 | 1992-02-11 | David J. Edlund | Thermally stable composite hydrogen-permeable metal membranes |
| JPH05137979A (en) * | 1991-11-25 | 1993-06-01 | Mitsubishi Kakoki Kaisha Ltd | Production of hydrogen separating membrane |
| JP3402515B2 (en) * | 1994-05-23 | 2003-05-06 | 日本碍子株式会社 | Hydrogen separator, hydrogen separator using the same, and method for producing hydrogen separator |
| DE19738513C1 (en) | 1997-09-03 | 1998-11-05 | Dbb Fuel Cell Engines Gmbh | Palladium alloy membrane foil for hydrogen separation |
| JP2002531246A (en) * | 1998-12-02 | 2002-09-24 | マサチューセッツ・インスティチュート・オブ・テクノロジー | Integrated palladium-based micromembrane for hydrogen separation and hydrogenation / dehydrogenation reactions |
| EP2128082A4 (en) * | 2007-02-19 | 2011-09-07 | Mitsubishi Gas Chemical Co | Hydrogen purification method, hydrogen separation membrane, and hydrogen purification apparatus |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51131473A (en) * | 1975-05-12 | 1976-11-15 | Masao Okubo | A process for manufacturing hydrogen permeable film |
| JPS62121616A (en) * | 1985-11-21 | 1987-06-02 | Ngk Insulators Ltd | Separating membrane of hydrogen gas |
-
1987
- 1987-06-26 JP JP16038287A patent/JPS644216A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51131473A (en) * | 1975-05-12 | 1976-11-15 | Masao Okubo | A process for manufacturing hydrogen permeable film |
| JPS62121616A (en) * | 1985-11-21 | 1987-06-02 | Ngk Insulators Ltd | Separating membrane of hydrogen gas |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004057993A (en) * | 2002-07-31 | 2004-02-26 | Dainippon Printing Co Ltd | Method of manufacturing hydrogen producing filter |
| JP4681201B2 (en) * | 2002-07-31 | 2011-05-11 | 大日本印刷株式会社 | HYDROGEN PRODUCTION FILTER AND ITS MANUFACTURING METHOD |
| WO2014126027A1 (en) | 2013-02-12 | 2014-08-21 | サンデン株式会社 | Showcase cooling device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS644216A (en) | 1989-01-09 |
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