WO1996000608A1 - Separateur de gaz et son procede de production - Google Patents

Separateur de gaz et son procede de production Download PDF

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Publication number
WO1996000608A1
WO1996000608A1 PCT/JP1994/001046 JP9401046W WO9600608A1 WO 1996000608 A1 WO1996000608 A1 WO 1996000608A1 JP 9401046 W JP9401046 W JP 9401046W WO 9600608 A1 WO9600608 A1 WO 9600608A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas
porous substrate
metal
separating
palladium
Prior art date
Application number
PCT/JP1994/001046
Other languages
English (en)
Japanese (ja)
Inventor
Tomonori Takahashi
Shinichi Kosaka
Original Assignee
Ngk Insulators, Ltd.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to JP07344993A priority Critical patent/JP3213430B2/ja
Priority claimed from JP07344993A external-priority patent/JP3213430B2/ja
Application filed by Ngk Insulators, Ltd. filed Critical Ngk Insulators, Ltd.
Priority to US08/602,845 priority patent/US5980989A/en
Priority to DE69421540T priority patent/DE69421540T2/de
Priority to EP94918591A priority patent/EP0715880B1/fr
Priority to PCT/JP1994/001046 priority patent/WO1996000608A1/fr
Publication of WO1996000608A1 publication Critical patent/WO1996000608A1/fr

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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
    • B01D71/022—Metals
    • B01D71/0223—Group 8, 9 or 10 metals
    • B01D71/02231—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0069—Inorganic membrane manufacture by deposition from the liquid phase, e.g. electrochemical deposition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • 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
    • B01D71/022—Metals
    • 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
    • C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion 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
    • 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
    • C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
    • C01B3/505—Membranes containing palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/46—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/04—Characteristic thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/22—Thermal or heat-resistance properties
    • 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
    • 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
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide

Definitions

  • the present invention relates to a gas separator for separating a specific gas from a mixed gas by diffusion, and a method for producing the same.
  • the separation membrane used in the membrane separation method includes a hydrogen separation membrane, an organic polymer membrane such as polyimide-polysulfone and an inorganic compound membrane such as palladium or palladium alloy membrane, and a silver or silver alloy membrane as the oxygen separation membrane.
  • a palladium or palladium alloy film has heat resistance and can obtain extremely high-purity hydrogen.
  • Palladium or palladium alloys have the property of dissolving and permeating hydrogen, making use of this property, and thin films made of palladium or palladium alloys are widely used in gas separators for separating hydrogen from mixed gas containing hydrogen. ing.
  • Japanese Patent Application Laid-Open No. 62-73030 discloses that there is no porous glass, porous ceramic, or porous aluminum oxide. Palladium or a palladium alloy is applied to the surface of the porous support to increase the mechanical strength of the palladium or palladium alloy thin film.
  • Japanese Unexamined Patent Publication No. Hei 3 (1994) -146612 discloses that a palladium thin film is formed on the surface of a heat-resistant porous substrate by a chemical plating method, and a silver thin film is formed on the palladium thin film by a chemical plating method. Then, a method for producing a hydrogen separator subjected to heat treatment is disclosed. In this production method, a hydrogen separator having a porous substrate and a palladium alloy thin film covering the porous substrate is obtained. By this heat treatment, palladium and silver are uniformly distributed in the palladium alloy thin film. ing.
  • U.S. Pat. No. 3,359,705 discloses a silver thin film for separating oxygen.
  • the source gas that undergoes gas separation through a defect that penetrates a gas separation membrane made of metal for separating gas (hereinafter referred to as a “penetration defect” as appropriate) is a purified gas.
  • ⁇ ⁇ has the disadvantage of leaking out. Therefore, the hydrogen concentration in the purified gas is reduced by the amount of the raw material gas.
  • the palladium film formed by the chemical plating has a defect penetrating the palladium thin film, and the source gas flows into the purified gas through the defect. Further, according to the method disclosed in this publication, a palladium film is formed on the surface of the porous body, but no palladium film is formed inside the small holes.
  • Japanese Patent Application Laid-Open No. 63-171716 discloses a method for producing a hydrogen separation membrane in which an inorganic porous membrane carries a palladium.
  • the inorganic porous membrane is made of palladium or a palladium alloy. It was deposited by-ring or the like, then, [P d (NH 3) 4] C 1 2 aqueous solution was vacuum degassed through an inorganic porous membrane, carrying Parajiumu and evaporated in inorganic porous membrane Is disclosed.
  • the hydrogen separation membrane not only transmits hydrogen but also transmits nitrogen, and thus the pores of the inorganic porous membrane are not closed by palladium.
  • the present invention has been made in view of the problems of the related art, and has as its object to provide a gas separator for preventing a raw material gas subjected to gas separation from leaking into a purified gas.
  • the present invention relates to a gas separator comprising a porous substrate having pores opened on the surface and a metal for separating gas, wherein the metal for separating gas is provided inside the pores.
  • a gas separator characterized by being filled and closed.
  • the metal for separating the gas covers at least a part of the surface of the porous substrate to form a thin film.
  • the depth of the metal for separating the gas into the inside of the porous substrate is 1 to 30 / m from the surface of the porous substrate.
  • the metal for separating the gas is preferably palladium, an alloy containing palladium as a main component, or an alloy containing palladium.
  • the porous substrate is immersed in a solution containing an activated metal while providing a pressure difference between a pair of surfaces of the porous substrate, whereby the pair of porous substrates is immersed in the solution.
  • An activation step of allowing the solution to penetrate into the pores opened on one of the surfaces, and attaching a metal for gas separation to the pores of the porous substrate by a chemical method This provides a method for producing a gas separator having a porous substrate having a pair of surfaces, characterized in that the gas for separating the gas fills and closes the small holes.
  • one surface of the porous substrate is subjected to a pressure applied to one surface thereof.
  • a solution containing an activated metal so that the pressure is greater than the pressure on one side of the porous substrate opposite to the surface of the porous substrate.
  • the solution is allowed to penetrate into the pores that are open in the pores, and a metal for gas separation is attached to the pores of the porous substrate in the chemical plating process, thereby forming a metal for gas separation.
  • the metal for separating the gas is preferably palladium, an alloy mainly containing palladium, or an alloy containing palladium.
  • FIG. 1 is an explanatory diagram showing a cross section of the gas separator of the present invention.
  • FIG. 2 is an explanatory diagram of a gas purification method using the gas separator of the present invention.
  • the gas separator 1 of the present invention has a porous substrate 2 and a metal 3 for separating gas. Since the porous substrate 2 is porous, it has a number of small holes 5 therein, and some of the small holes are connected to the surface of the porous substrate 2 and open. Therefore, in the present invention, the metal 3 for separating the gas fills and closes the inside of the small holes 5 opened in the porous substrate surface 2a. Thereby, when the raw material gas subjected to gas separation by the gas separator 1 passes through the small holes 5 of the porous substrate 2, it passes through the metal 3 for separating the gas, and the gas is separated.
  • the metal 3 for separating the gas fills and closes the inside of the small hole 5
  • the raw material gas does not leak to the refined gas side. Therefore, for example, with the gas separator of the present invention using a palladium alloy, hydrogen gas having a purity of 99% or more can be obtained, and usually, hydrogen gas having a purity of 99.9% or more can be obtained. Can be obtained.
  • the raw material gas does not react.
  • alumina silica, silica-alumina, mullite, kojierite, zirconia, and the like
  • Porous metal, porous glass and the like can be used.
  • This porous substrate has a large number of fine pores that are continuous in three dimensions.
  • the pore size is preferably 0.003 to 20 Zm, more preferably 0.005 to 5 // m, and furthermore, 0.0 1 to 1 m is preferred. If the pore diameter is less than 0.003 m, the resistance when the gas passes will be large. On the other hand, if the pore diameter exceeds 20 m, the reaction time becomes too long when metal 3 for separating gas is attached to the pores by chemical plating, filled, and blocked, which is not desirable. is there. In addition, when there is a membrane covering the porous substrate 2, that is, when there is the gas separation membrane 4, pinholes are easily formed in the gas separation membrane 4, which is not preferable. Such a porous substrate can be obtained, for example, by the method described in JP-A-62-273030.
  • the pores of the porous substrate have a uniform pore diameter.
  • the thickness of the porous substrate 2 is not particularly limited, as long as sufficient mechanical strength can be maintained in a use environment.
  • the porous substrate 2 preferably has a planar shape.
  • the planar shape includes a flat surface and a curved surface, and naturally includes a tubular shape corresponding to a shape having a closed curved surface.
  • the cross-sectional shape of the pipe is arbitrary, but a circular one is preferred because it is easily available.
  • the shape of the gas separator or the shape of the porous substrate 2 may be plate-like, and may be any shape depending on the purpose of use. Further, it is preferable that the porous substrate has a pair of surfaces.
  • the metal 3 for separating the gas is selected according to the gas to be purified.
  • the gas to be purified for example, palladium, an alloy containing palladium as a main component, or an alloy containing palladium is used.
  • a thin film of silver or an alloy containing silver as a main component, an organic material thin film, or the like is used.
  • the metal 3 for separating the gas fills and closes the inside of the small hole 5 opened on the surface 2 a of the porous substrate 2.
  • the metal 3 covers the surface 2 a of the porous substrate 2 to form the gas separation membrane 4.
  • the metal 3 for separating the gas inside the porous substrate 2 performs the function of gas separation, so that the gas separation membrane 4 as shown in FIG. Not required.
  • the porous substrate surface 2a may be covered. This is because the purified gas more securely permeates the metal 3 for separating the gas at the portion where the gas is coated. It is preferable that the gas separation membrane 4 covers the porous substrate surface 2a. As shown in FIG. 1, the metal 3 for filling the inside of the small holes opened on the surface of the porous substrate and separating the gas that blocks the gas is used to separate the gas forming the gas separation membrane 4. Preferably, the metal is continuous. This improves the adhesion between the gas separation membrane 4 and the porous substrate, and makes it difficult for the gas separation membrane 4 to peel off from the porous substrate surface 2a.
  • the thickness of the gas separation membrane 4 is preferably 50 m or less, and more preferably 2 O ⁇ m or less. If the thickness exceeds 5 ⁇ , the time required for the source gas to diffuse through the gas separation membrane during gas separation by the gas separator becomes longer, and the processing time becomes longer, which is not preferable.
  • the depth of the metal 3 for separating gas into the inside of the porous substrate 2 is preferably 1 to 30 m from the above surface of the porous substrate, and 1 to 20 / m. More preferably, it is even more preferably 1 to 10 m. If the depth is smaller than 1 / xm, the pores are not sufficiently blocked by the metal 3 for separating the gas, and the source gas may leak to the purified gas side. Further, when the gas separation membrane 4 is formed, the gas separation membrane 4 is easily separated from the porous substrate surface 2a. On the other hand, if the depth is greater than 30 m, the gas separated by the gas separator 1 takes a long time to diffuse in the metal 3 for separating gas, This is because the separation time is long and is not preferred.
  • the surface 2a of the porous substrate in which the metal 3 for separating gas is filled in the pores is located outside the tubular porous substrate. It may be inside.
  • the metal 3 for separating gas is made of a palladium alloy
  • the content of metals other than palladium is preferably from 10 to 30% by weight.
  • the main purpose of alloying palladium is to prevent hydrogen embrittlement of palladium and to improve the separation efficiency at high temperatures. Further, it is preferable to contain silver as a metal other than palladium in order to prevent hydrogen embrittlement of palladium.
  • the method for producing a gas separator according to the present invention includes an activation step and a chemical plating step.
  • the activation step one surface of the porous substrate is immersed in a solution containing an activated metal so that the pressure applied to one surface is greater than the pressure applied to the other surface on the opposite side of the porous substrate.
  • the solution is allowed to penetrate into the pores opened on the surface of one side of the porous substrate where the pressure is higher. Due to such a pressure difference, the activated metal not only adheres to the surface of the porous substrate, but also adheres to the inner surface of the pores opened on the surface of the porous substrate. .
  • a metal for gas separation is deposited on the surface to which the activated metal has adhered.
  • a tube-shaped porous substrate can be used, the outside of which is immersed in a solution containing an activated metal, and the inside of the tube can be pulled by a vacuum pump.
  • a tube-shaped porous substrate may be used, and its outside may be immersed in a solution containing an activated metal, and a pressure may be applied to this solution to keep the inside of the tube at a constant pressure. In either case, the outside and inside of the tube can be reversed, so that the solution is immersed inside the tube and the pressure can be changed.
  • the activating metal a compound containing a palladium divalent ion can be suitably used.
  • the porous substrate can be alternately immersed in an aqueous hydrochloric acid solution of palladium chloride and an aqueous hydrochloric acid solution of tin chloride, and the porous substrate can be immersed in either of these solutions. It is preferable to maintain a specified pressure difference even when In the next chemical measurement, electroless plating is performed using a plating solution containing at least a metal for separating gas and a reducing agent, and the metal for separating gas is used as pores in the porous substrate. The metal for gas separation fills and closes the pores.
  • one side treated in the activation process is processed. For example, replacing the above solution used in the activation process with an appropriate plating solution Can be.
  • At least a gas is applied to one surface of the porous substrate in a manner similar to that of the activation process so that the pressure applied to one surface is greater than the pressure applied to the opposite surface of the porous substrate. It is preferable to immerse in a plating solution containing a metal for separation and a reducing agent. This pressure difference facilitates the penetration of the plating solution into the inside of the small holes opened on the surface of the porous substrate. As described above, the portion to which the activation metal has adhered in the activation step is damaged.
  • the immersion time in the chemical plating process By adjusting the immersion time in the chemical plating process, the temperature of the plating solution, the pressure difference between the two surfaces of the porous substrate, etc., the depth at which the metal for gas separation enters the surface of the porous substrate can be reduced. Can be adjusted.
  • a known chemical plating solution containing palladium For hydrogen separation, use a known chemical plating solution containing palladium, and for oxygen separation, use a known chemical plating solution containing, for example, silver nitrate, EDTA, aqueous ammonia, and hydrazine. .
  • palladium is chemically plated, silver is further plated on the surface of the electrodeposited palladium, and then heat treatment is performed to allow palladium and silver to interact with each other. It is preferred to diffuse and alloy palladium and silver.
  • the porous substrate was activated.
  • a porous ⁇ -alumina tube having a cylindrical shape with an outer diameter of 10 mm, an inner diameter of 7 mm, and a length of 300 mm and a fine pore diameter of 0.1 m was used as the porous substrate.
  • the outer surface of the alumina tube, the SnCl 2 ⁇ 2 ⁇ 2 0 0. 1 you content wt% 0. was immersed crushed 1 minute 1% aqueous hydrochloric acid solution, while, pull the inside of the tube by a vacuum pump, The pressure was reduced.
  • the outer surface of the tube was immersed in a 0.1% hydrochloric acid aqueous solution containing 0.01% by weight of PdCl 2 for 1 minute. When immersing, the inside of the tube was pulled with a vacuum pump to reduce the pressure. This immersion treatment was repeated with both hydrochloric acid aqueous solutions so as to be immersed 10 times in each hydrochloric acid aqueous solution.
  • the mixture was kept at 900 ° C. for 12 hours to perform a heat treatment to mutually diffuse palladium and silver, thereby alloying palladium and silver to obtain a gas separator.
  • a hydrogen separation test was performed on the gas separator.
  • a mixed gas consisting of 80% by volume of hydrogen and 20% by volume of carbon dioxide was used as a source gas.
  • Figure 2 shows a schematic diagram of the test equipment.
  • the chamber 7 was heated to 500.
  • the above mixed gas 17 having a pressure of 9 k'g weight cm 2 is applied to the outside of the alumina tube 6 at 2 N liters per minute (that is, the volume at room temperature is 2 liters). Introduced.
  • 0.1 N liter / min was introduced into the inside of the alumina tube as a sweep gas 18 of argon having a pressure of lkg weight Zcm 2 .
  • Quantitative analysis was performed on the purified gas 19 obtained by gas chromatography to examine the gas permeation rate of the purified gas and the hydrogen concentration in the purified gas.
  • the mixed gas 17 to be separated is introduced from the introduction pipe 10 to the outside of the gas separator 16. Further, the sweep gas 18 of the separated hydrogen gas is introduced into the gas separator 16 from the introduction pipe 8. o — Rings 15 surround the outer surfaces at both ends of the separator 16 to prevent gas leakage.
  • the gas permeation rate per cm 2 and per minute of the palladium membrane on the gas separator was 18 m 1
  • the hydrogen purity of the purified gas 19 was 99.9% or more. .
  • Table 1 shows the test results of the airtightness test, gas separation test and heat cycle test.
  • Example 1 1 5 5 0.
  • Comparative example 3 5 0 .5 1 1 7 0 84 No change
  • the heat cycle test is also one of the parameters indicating the adhesion of the gas separation membrane to the porous substrate in the gas separator. Comparing the example with the comparative example, it can be seen that in the example, the gas separation membrane is less likely to be peeled from the porous substrate, and the adhesion between the gas separation membrane and the porous substrate is improved. This is because in the example, the metal for separating the gas fills and closes the inside of the small holes opened on the surface of the porous substrate.
  • the metal for separating the gas fills and closes the inside of the small holes opened on the surface of the porous substrate, whereby the raw material gas subjected to gas separation by the gas separator is There is no leakage to the purified gas side. Therefore, for example, with the gas separator of the present invention using a palladium alloy, hydrogen gas having a purity of 99.9% or more can be obtained.
  • the gas separator of the present invention has a gas separation membrane made of a metal for separating gas on the surface of the porous substrate, the pores in which the metal for separating gas is opened on the surface of the porous substrate. Since the inside of the cell is filled and closed, the adhesion between the gas separation membrane and the porous substrate can be improved. This is remarkable when compared with a gas separator in which the gas separation membrane covers the surface of the porous substrate without filling the pores opened in the surface of the porous substrate.
  • the porous substrate having a pair of surfaces contains an activated metal while providing a pressure difference between the pair of surfaces. Immerse in the solution. As a result, the solution penetrates into the small holes opened on one surface.
  • a metal for separating gas is attached to the small holes of the porous substrate, whereby the metal for separating gas fills and closes the small holes.
  • a specific gas such as hydrogen can be obtained with high purity from a mixed gas.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Dispersion Chemistry (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

Dans un séparateur de gaz, d'un métal de séparation remplit et obture de petite cavités ouvertes pratiquées à la surface d'un corps de base poreux, ce qui supprime tout risque de fuite du gaz de départ vers le gaz raffiné. Le procédé de production dudit séparateur de gaz consiste dans l'activation par immersion d'un corps de base poreux présentant deux surfaces dans une solution contenant un métal d'activation, tout en exerçant une différence de pression entre les deux surfaces, et en procédant à un placage chimique pour amener le métal de séparation à remplir et obturer les petites cavités du corps de base poreux.
PCT/JP1994/001046 1993-03-31 1994-06-28 Separateur de gaz et son procede de production WO1996000608A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP07344993A JP3213430B2 (ja) 1993-03-31 1993-03-31 ガス分離体及びその製造方法
US08/602,845 US5980989A (en) 1993-03-31 1994-06-28 Gas separator and method for preparing it
DE69421540T DE69421540T2 (de) 1994-06-28 1994-06-28 Methode zur Herstellung einer Gastrennvorrichtung
EP94918591A EP0715880B1 (fr) 1994-06-28 1994-06-28 Procédé de production d'un séparateur de gaz
PCT/JP1994/001046 WO1996000608A1 (fr) 1993-03-31 1994-06-28 Separateur de gaz et son procede de production

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP07344993A JP3213430B2 (ja) 1993-03-31 1993-03-31 ガス分離体及びその製造方法
PCT/JP1994/001046 WO1996000608A1 (fr) 1993-03-31 1994-06-28 Separateur de gaz et son procede de production

Publications (1)

Publication Number Publication Date
WO1996000608A1 true WO1996000608A1 (fr) 1996-01-11

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5989319A (en) * 1996-07-08 1999-11-23 Ngk Insulators, Ltd. Gas separator
US6066592A (en) * 1996-07-08 2000-05-23 Ngk Insulators, Ltd. Gas separator

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2824620A (en) * 1955-09-12 1958-02-25 Universal Oil Prod Co Purification of hydrogen utilizing hydrogen-permeable membranes
US4496373A (en) * 1981-12-11 1985-01-29 Kernforschungsanlage Julich Gesellschaft Mit Beschrankter Haftung Diffusion membrane and process for separating hydrogen from gas mixture
JPH03288534A (ja) * 1990-04-04 1991-12-18 Ebara Corp 無電解Ｐｄ―Ａｇ合金メッキ膜を有する水素分離膜及びその製造方法
JPH05285356A (ja) * 1992-04-08 1993-11-02 Mitsubishi Heavy Ind Ltd 水素分離膜の製造方法
JPH06114230A (ja) * 1992-10-07 1994-04-26 Ngk Insulators Ltd ガス分離体の製造方法
JPH06142471A (ja) * 1992-01-02 1994-05-24 Air Prod And Chem Inc 有機金属化学蒸気浸透による無機膜の製法
JPH06277472A (ja) * 1993-03-31 1994-10-04 Ngk Insulators Ltd ガス分離体及びその製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2824620A (en) * 1955-09-12 1958-02-25 Universal Oil Prod Co Purification of hydrogen utilizing hydrogen-permeable membranes
US4496373A (en) * 1981-12-11 1985-01-29 Kernforschungsanlage Julich Gesellschaft Mit Beschrankter Haftung Diffusion membrane and process for separating hydrogen from gas mixture
JPH03288534A (ja) * 1990-04-04 1991-12-18 Ebara Corp 無電解Ｐｄ―Ａｇ合金メッキ膜を有する水素分離膜及びその製造方法
JPH06142471A (ja) * 1992-01-02 1994-05-24 Air Prod And Chem Inc 有機金属化学蒸気浸透による無機膜の製法
JPH05285356A (ja) * 1992-04-08 1993-11-02 Mitsubishi Heavy Ind Ltd 水素分離膜の製造方法
JPH06114230A (ja) * 1992-10-07 1994-04-26 Ngk Insulators Ltd ガス分離体の製造方法
JPH06277472A (ja) * 1993-03-31 1994-10-04 Ngk Insulators Ltd ガス分離体及びその製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, Vol. 33, No. 3, March 1994, WASHINGTON, US, Page 616-622, S. YAN et al., "Thin palladium membrane formed in support pores by metal organic chemical vapor deposition method and application to hydrogen separation". *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5989319A (en) * 1996-07-08 1999-11-23 Ngk Insulators, Ltd. Gas separator
US6066592A (en) * 1996-07-08 2000-05-23 Ngk Insulators, Ltd. Gas separator

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