WO2011122414A1 - Filtre poreux, son procédé de production, membrane de séparation de l'hydrogène avec filtre poreux utilisé comme support, procédé de colmatage de défauts et procédé de séparation de l'hydrogène - Google Patents

Filtre poreux, son procédé de production, membrane de séparation de l'hydrogène avec filtre poreux utilisé comme support, procédé de colmatage de défauts et procédé de séparation de l'hydrogène Download PDF

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WO2011122414A1
WO2011122414A1 PCT/JP2011/056977 JP2011056977W WO2011122414A1 WO 2011122414 A1 WO2011122414 A1 WO 2011122414A1 JP 2011056977 W JP2011056977 W JP 2011056977W WO 2011122414 A1 WO2011122414 A1 WO 2011122414A1
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palladium
thin film
metal
hydrogen
porous
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PCT/JP2011/056977
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English (en)
Japanese (ja)
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安行 松村
崇志 前田
稔 小川
英二 根岸
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独立行政法人産業技術総合研究所
Ｊｘ日鉱日石エネルギー株式会社
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Priority to JP2012508234A priority Critical patent/JP5891512B2/ja
Publication of WO2011122414A1 publication Critical patent/WO2011122414A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/10—Testing of membranes or membrane apparatus; Detecting or repairing leaks
    • B01D65/106—Repairing membrane apparatus or modules
    • B01D65/108—Repairing 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
    • 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
    • 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
    • B01D2323/28—Pore treatments
    • B01D2323/286—Closing of pores, e.g. for membrane sealing
    • 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

Definitions

  • the present invention relates to a porous filter, a manufacturing method thereof, a hydrogen separation membrane using the porous filter as a support, a defect sealing method, and a hydrogen separation method.
  • Porous ceramic membranes are used for gas or liquid filtration, and those in which a thin film of palladium or palladium alloy is formed thereon are used as hydrogen separation membranes.
  • the pore diameter on the surface of the porous ceramic film varies depending on the application, it is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less for the purpose of removing impurities. Even when the porous ceramic film is used as a support of a palladium or palladium alloy thin film, the pore diameter is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less. In any application, it is necessary that the permeation rate of gas or liquid passing through the porous ceramic membrane is high, but such micropores have high permeation resistance, and therefore porous ceramics having micropores. It is necessary to reduce the film thickness.
  • the present invention has been made in view of the current state of the prior art described above, and an object thereof is to provide a porous filter free from surface defects and a method for producing the same.
  • a palladium thin film or a palladium alloy thin film that is highly useful as a hydrogen separation membrane is formed on a porous ceramic support without defects, and the amount of expensive palladium used is reduced.
  • an object of the present invention is to provide a hydrogen separation membrane that achieves both a high hydrogen permeation rate and high hydrogen selectivity, and to provide a method for efficiently separating hydrogen using the hydrogen separation membrane.
  • the present inventor has intensively studied to achieve the above-mentioned purpose.
  • the plating solution containing metal ions on the other side of the porous ceramic film is moved to one side of the porous ceramic film by osmotic pressure, and the metal is deposited on one side of the porous ceramic film. It is possible to close surface defects with metal without blocking fine pores, and forming a thin palladium film or palladium alloy thin film on the surface of the ceramic filter formed in this way as a support provides a good hydrogen separation membrane.
  • the plating solution containing metal ions on the other side of the palladium alloy thin film precursor is moved to one side of the palladium alloy thin film precursor by osmotic pressure, and To find out that defects can be blocked by depositing metal on the direction side, to complete the present invention was Tsu.
  • the object of the present invention is achieved by a porous filter characterized in that a defect opened on one surface of a porous ceramic film is closed by a metal.
  • the metal closing the defect is palladium and / or copper.
  • the object of the present invention is to provide a solvent in which a solute and / or a reducing agent on one side of the porous ceramic film is dissolved, and a plating solution containing metal ions on the other side of the porous ceramic film.
  • the method is achieved by a method for manufacturing a porous filter, wherein the plating solution is moved to one side of the porous ceramic film by osmotic pressure, and the metal is deposited on one side of the porous ceramic film.
  • the object of the present invention is achieved by a hydrogen separation membrane in which a palladium thin film or a palladium alloy thin film is formed on one surface of the porous filter.
  • the object of the present invention is to provide a solvent that dissolves a solute and a reducing agent on one side of a metal film that is a precursor of the palladium alloy thin film, and a metal that constitutes the palladium alloy thin film on the other side of the metal film.
  • the plating solution is moved to one surface side of the metal film by osmotic pressure with a plating solution containing no reducing agent and containing the ions, and the metal ions are reduced and deposited on the one surface side of the metal film.
  • the object of the present invention is characterized in that the hydrogen-containing mixed gas is positioned on one side through the hydrogen separation membrane, and the hydrogen partial pressure on the other side is made equal to or lower than the hydrogen partial pressure on the hydrogen-containing mixed gas side. This is achieved by a method for separating hydrogen from a hydrogen-containing gas mixture.
  • a porous filter in which the surface defects of the ceramic porous body are closed with metal can be obtained by a relatively simple method. Moreover, by using this porous filter as a base material, a palladium or palladium alloy thin film having no defect can be formed even when the average film thickness is thin. This method does not require a large-scale manufacturing facility, and is extremely useful because it is free from strict control of processes and poor yield and facilitates mass production.
  • the resulting porous filter can avoid a decrease in fractionation performance due to defects, and the hydrogen separation membrane has a defect-free palladium or palladium alloy thin film, so that gases other than hydrogen can permeate. It can be effectively prevented and has excellent hydrogen selective permeability, and can be used very effectively as a hydrogen separation membrane for separating hydrogen from a gas mixture containing hydrogen.
  • (A) is a digital microscope observation photograph of the defective part in the porous filter before osmotic plating
  • (b) is a digital microscope observation photograph of the defective part in the porous filter after osmotic plating. is there. It is a scanning electron micrograph of the defective part in the porous filter after performing osmotic pressure plating.
  • the porous filter of the present invention is a porous ceramic thin film obtained by sintering ceramic fine particles, and is characterized in that a defect site such as a crack opened on the surface or a defect due to peeling is blocked by a metal.
  • a defect site such as a crack opened on the surface or a defect due to peeling is blocked by a metal.
  • the material for the porous ceramic thin film include yttrium-stabilized zirconium oxide, zirconium oxide, cerium oxide, zirconia-ceria, alumina, silica, and titanium oxide.
  • the pore diameter of the porous ceramics should be appropriately selected depending on the application, but is preferably 0.02 to 1.0 ⁇ m, more preferably 0.05 to 0.5 ⁇ m.
  • porous ceramic thin film is required to maintain a good gas or liquid permeation rate, and is usually rougher, since the film thickness is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less.
  • a porous substrate in addition to ceramics such as yttrium-stabilized zirconium oxide, zirconium oxide, cerium oxide, zirconia-ceria, alumina, silica, and titanium oxide, porous metal such as sintered metal and metal mesh may be used.
  • porous metal material include stainless steel, hastelloy alloy, inconel alloy, nickel, nickel alloy, titanium, titanium alloy, and the like.
  • the porous ceramic thin film may be formed in a form filled in the surface pores.
  • the thickness of the porous substrate there is no particular limitation on the thickness of the porous substrate, and it is only necessary that the structure can be stably maintained.
  • shape of a porous filter For example, shapes, such as plate shape, a hollow tubular shape, and a bottomed cylindrical shape, are employable.
  • the porous ceramic thin film may be held on the porous substrate by a known method.
  • a dispersion slurry of ceramic fine particles or a sol-like or gel-like ceramic fine particle precursor may be coated on a porous substrate by a method such as spraying, screen printing, or dipping, or by electrophoretic deposition or gas deposition. Such a method may be used.
  • the metal that closes and / or covers the surface defects of the porous ceramic thin film is not particularly limited, and may be appropriately selected depending on the application, but palladium, gold, platinum, rhodium, ruthenium, silver, nickel, cobalt, chromium, Examples thereof include copper, iron, tin and mixtures thereof.
  • the thickness of the metal that closes the defect is not necessarily limited by the shape and size of the defect, but is preferably 0.1 to 10 ⁇ m, more preferably 0.3 to 5 ⁇ m.
  • electroless plating of metals the application of electroless plating catalyst fine particles to the object to be plated and the reduction of the plating catalyst fine particles usually precede electroless plating in an electroless plating solution containing metal ions and a reducing agent. Done. On the surface of the object to be plated in the electroless plating solution, a reduction reaction of metal ions first occurs due to the applied catalyst fine particles, and the catalyst fine particles serve as nuclei to cause growth of the metal to be plated.
  • known electroless plating reagents may be used.
  • an object to be plated is put in a solution containing metal ions such as tin ions, and metal ions such as tin ions are adsorbed on the surface of the object to be plated, and then a catalyst containing palladium ions.
  • metal ions such as tin ions attached to the surface with palladium ions in the solution
  • a method in which palladium ions are directly placed in a solution (alkali catalyst) that adheres to an object to be plated and then reduced.
  • the above-mentioned electroless plating catalyst fine particle is applied to one surface of the porous ceramic thin film, and then the plating catalyst fine particle is reduced. I do.
  • the electroless plating solution is placed on the other side (porous substrate side) of the porous ceramic thin film, and the electroless plating solution is supplied to one side of the porous ceramic thin film through the pores of the porous ceramic.
  • the electroless plating solution can be moved to one side of the porous ceramic thin film by making the pressure on the other side (porous substrate side) of the porous ceramic thin film higher than the pressure on the one side of the thin film.
  • a solvent in which a solute is dissolved is placed on one side of the ceramic thin film and an osmotic pressure is generated, it can be carried out simply and efficiently.
  • Any solvent may be used as long as it is compatible with the electroless plating solution used and does not adversely affect the electroless plating. Examples thereof include water, alcohols such as methanol, ethanol, and propanol, and mixtures thereof.
  • the solute is not particularly limited as long as it has high solubility in a solvent and does not adversely affect electroless plating, and examples thereof include sugars such as glucose and sucrose, and salts such as sodium chloride and potassium chloride.
  • the concentration of the solution may be determined in consideration of the supply rate to the defects of the electroless plating solution, but is usually about 0.5 to 10 mol / L.
  • the same effect can be obtained by using a plating solution containing no reducing agent instead of the electroless plating solution and dissolving the reducing agent in a solvent in which the solute on one surface of the porous ceramic thin film is dissolved.
  • the electroless plating solution is separated and stored in a solution containing a metal ion and a solution containing a reducing agent, and mixed before use for plating. Then, you may use the solution containing the metal ion before mixing as a plating solution which does not contain a reducing agent.
  • ascorbic acid sodium ascorbate, sodium borohydride, potassium borohydride, dimethylaminoborane, trimethylaminoborane, citric acid, sodium citrate, formic acid, sodium formate, tannic acid, glyoxylic acid, diborane, hydrazine , Formaldehyde and the like can be exemplified, but there is no particular limitation as long as it is a drug capable of reducing metal ions.
  • the liquid permeation rate of the defective part existing on one surface of the porous ceramic thin film is much higher than the permeation rate of the non-defect part, an electroless plating solution or a plating solution containing no reducing agent is selectively supplied to the defective part.
  • metal selectively deposits on the defect and closes the defect.
  • the state of the blockage differs depending on the state of the defect. For example, if the small part of the ceramic thin film is peeled off, the outflow amount of the electroless plating solution or metal ion solution increases, so the defective part is covered with metal. The In addition, when the defect is relatively small, the outflow amount of the electroless plating solution or the plating solution not containing the reducing agent is reduced, resulting in metal deposition inside the defect.
  • the hydrogen separation membrane of the present invention has a palladium thin film or a palladium alloy thin film formed on a porous filter in which defects are closed with the above metal as a support.
  • the palladium alloy thin film is preferably an alloy of palladium and one or more metals selected from the group consisting of silver, gold, copper, nickel, platinum, rhodium and ruthenium.
  • the proportion of palladium in such a palladium alloy is preferably 40% by weight or more.
  • the average film thickness of the palladium thin film or palladium alloy thin film is preferably from 0.1 to 10 ⁇ m, more preferably from 0.2 to 5 ⁇ m. If the film thickness is smaller than this, the pinholes of the film increase and the hydrogen selectivity as a hydrogen separation membrane is lowered. If the film thickness is larger than this, the hydrogen permeation rate is reduced and the utility is lost.
  • the metal closing the defect of the porous filter is preferably one or two or more metals selected from the group consisting of palladium, silver, gold, copper, nickel, platinum, rhodium and ruthenium. And / or copper.
  • the metal closing the defect becomes part of the palladium thin film or palladium alloy thin film formed thereon. That is, the metal film thickness on the defect substantially matches the sum of the average film thickness of the palladium thin film or the palladium alloy thin film and the thickness of the metal blocking the defect.
  • the formation of the palladium thin film or the palladium alloy thin film on the porous filter in which the defect is closed with a metal may be performed by a known method such as electroless plating, chemical vapor deposition, or magnetron sputtering. Is the simplest.
  • the fine particles for electroless plating are applied to the support and reduced.
  • this step may be omitted when the support is a porous filter whose defects are closed with palladium. If the metal that closes the defect contains something that is more base than palladium, that is, if it contains silver, nickel, cobalt, chromium, copper, iron, tin, immerse the porous filter in a solution containing palladium ions. Alternatively, a base metal than palladium may be replaced with palladium. Moreover, you may combine this substitution plating process and the electroless-plating catalyst fine particle provision and reduction process.
  • the metal layer which is a precursor of a palladium thin film or a palladium alloy thin film is formed by electroless plating.
  • This electroless plating solution may be a known one.
  • the electroless plating solution may be placed on one side of the porous ceramic thin film, that is, on the surface where the metal is deposited.
  • the electroless plating of the metal layer that is the precursor of the palladium thin film or the palladium alloy thin film is followed by the formation of a metal that forms the palladium alloy thin film, and then alloyed by heat treatment. Also good.
  • the pinhole generation of a palladium thin film or palladium alloy thin film formed on the support is more than when a conventional ceramic porous material is used as the support.
  • the film thickness can be reduced as compared with the conventional case.
  • a metal layer which is a precursor of a palladium thin film or a palladium alloy thin film is formed on the support by electroless plating as a first stage of plating of palladium or palladium alloy on the support. Then, when the metal layer as the precursor substantially covers the surface of the support, the pressure on the side in contact with the plating solution of the first-stage plating film as the formation of the second-stage metal film is the other support The plating solution is allowed to enter the remaining defects so as to be higher than the pressure on the body side. As a result, deposition of a metal that forms a palladium or palladium alloy thin film inside the defect occurs, and the defect can be efficiently blocked.
  • the metal species to be plated in the second stage may be different from that in the first stage.
  • the electroless plating catalyst fine particle applying step may be performed again after completion of the first stage electroless plating.
  • the catalyst solution may be introduced into the defect so that the pressure on one side contacting the catalyst solution of the porous ceramic support (porous filter) is larger than the pressure on the other side.
  • the pressure on one side of the porous ceramic support (porous filter) in contact with the solution containing the reducing agent is greater than the pressure on the other side so that the solution is within the defect. Should be introduced.
  • a metal film for forming a palladium alloy thin film may be further formed.
  • plating can be performed using the same method as in the second stage, and a known film formation method such as a normal plating method, chemical vapor deposition method, or magnetron sputtering can also be used. This subsequent film formation may be repeated.
  • defects may remain even after the second stage film formation, and even if a metal film is further formed thereon, the defects may not be efficiently removed.
  • a plating solution that does not contain a reducing agent is placed on the other side (support side) of the film, and the reducing agent is passed through the defect pores.
  • a plating solution containing no is supplied to one side of the metal film.
  • the metal film can be moved to one side by increasing the pressure on the other side of the metal film to be higher than the pressure on the one side of the metal film, but placing a solvent that dissolves the solute on the one side of the metal film.
  • osmotic pressure When osmotic pressure is generated, it can be carried out easily and efficiently.
  • the reducing agent is dissolved in this solvent.
  • the metal deposits at the site where the plating solution not containing the reducing agent at the defect site and the reducing agent are associated, and the defect can be effectively blocked.
  • a normal electroless plating solution can be used instead of a plating solution that does not contain a reducing agent.
  • the reducing agent is contained in the electroless plating solution, a metal film is formed on the other side of the formed metal film. Precipitation may occur, which is not preferable.
  • any solvent may be used as long as it is compatible with the plating solution not containing the reducing agent to be used and does not adversely affect the metal deposition.
  • examples thereof include water, alcohols such as methanol, ethanol, and propanol, and mixtures thereof.
  • the solute is not particularly limited as long as it has high solubility in a solvent and does not adversely affect the reduction and precipitation of metal ions, and examples thereof include sugars such as glucose and sucrose, and salts such as sodium chloride and potassium chloride.
  • the concentration of the solution may be determined in consideration of the supply rate to the defects of the solution containing metal ions, but it is usually about 0.5 to 10 mol / L.
  • the metal ions contained in the plating solution not containing the reducing agent may be any metal constituting the palladium alloy film, that is, any ion of palladium, silver, gold, copper, nickel, platinum, rhodium and ruthenium.
  • Ascorbic acid, sodium ascorbate, sodium borohydride, potassium borohydride, dimethylaminoborane, trimethylaminoborane, citric acid, sodium citrate, formic acid, sodium formate, tannic acid, glyoxylic acid, diborane, hydrazine , Formaldehyde and the like can be exemplified, but there is no particular limitation as long as it is a drug capable of reducing metal ions.
  • the metal film contains palladium
  • a metal film containing palladium and a solvent containing a reducing agent come into contact with each other, the generated hydrogen may cause embrittlement of the metal film containing palladium and destroy the metal film.
  • This defect sealing method of a metal film can be applied not only to the production of a palladium alloy film using a porous filter in which defects are closed with a metal as a support, but also to the production of a palladium alloy film on a normal support. Applicable.
  • a metal film for forming a palladium alloy thin film may be further formed.
  • plating can be performed using the same technique as in the second step, and a known film formation technique such as a normal plating method, chemical vapor deposition method, or magnetron sputtering can also be used. This subsequent film formation may be repeated.
  • a palladium thin film When a palladium thin film is formed on a porous filter in which defects are closed with a metal, it can be used as it is as a hydrogen separation membrane, but it is preferable to perform heat treatment because the performance is stabilized.
  • heat treatment when the metal forming the palladium alloy is formed into a layer, heat treatment is required to obtain a complete alloy state, and some heat treatment is required even when the palladium alloy is directly formed.
  • This heat treatment can usually be performed by heating in a reducing gas atmosphere or an inert gas atmosphere.
  • the reducing gas for example, a reducing gas such as hydrogen, carbon monoxide, or methanol can be used.
  • the inert gas include helium, nitrogen, and argon. Alternatively, it may be performed under vacuum.
  • the treatment temperature can be appropriately set, but is preferably about 300 to 800 ° C., particularly preferably 400 to 700 ° C.
  • the upper limit temperature of the heat treatment is determined in consideration of the heat resistance of the porous ceramic or sintered metal (when used as a porous ceramic support). In order to remove organic substances adhering to the surface of the hydrogen separation membrane during the treatment, it may be brought into contact with oxygen or a gas containing oxygen.
  • the hydrogen separation membrane configured as described above can be used for separating only hydrogen from a mixed gas containing hydrogen according to a conventional method.
  • a hydrogen-containing mixed gas is positioned on any one side separated by the hydrogen separation membrane, one surface of the hydrogen separation membrane is brought into contact with the hydrogen-containing gas, and hydrogen on the other surface side of the hydrogen separation membrane is
  • the partial pressure may be set to be equal to or lower than the hydrogen partial pressure on the hydrogen-containing mixed gas side.
  • hydrogen selectively permeates through the hydrogen separation membrane, and only hydrogen on the hydrogen-containing mixed gas side can be moved to the opposite side for separation.
  • the temperature of the hydrogen separation membrane is usually about 150 ° C. to 700 ° C., preferably about 300 ° C. to 600 ° C. If the temperature is too low, embrittlement of the palladium or palladium alloy thin film tends to occur, and if the temperature is too high, the film tends to deteriorate, which is not preferable.
  • Example 1 Thickness of 30 ⁇ m, average pore diameter produced by coating yttrium-stabilized zirconium oxide particles on the outer surface of a bottomed cylindrical stainless steel sintered metal filter (filter length: 5cm, filter diameter: 1cm) with the inside and outside isolated
  • a porous filter on which a 0.1 ⁇ m ceramic porous thin film (porous ceramic film) was formed was immersed in a commercially available alkaline catalyst at 50 ° C. to allow palladium ions to adhere to the outer surface. Reduced in reducing solution.
  • FIG. 1A is a digital microscope observation photograph of a defect portion in the ceramic porous thin film before osmotic plating
  • FIG. 1B is a defect in the ceramic porous thin film after osmotic plating. It is a digital microscope observation photograph of a part. This defective portion is a portion of a non-uniform ceramic porous body generated when the ceramic porous thin film is formed, and it is considered that a crack is partially present. Further, it was confirmed by scanning electron microscope observation that there was no blockage of pores of 0.3 ⁇ m or less by palladium.
  • Example 2 A porous filter in which silver was deposited in the defective part was obtained in the same manner as in Example 1 except that a commercially available electroless silver plating solution was used instead of the electroless palladium plating solution of Example 1. As a result of observing with a digital microscope after drying, it was confirmed that the defective part was discolored by silver. Further, it was confirmed by scanning electron microscope observation that there was no blockage of pores of 0.3 ⁇ m or less by silver.
  • FIG. 2 is a scanning electron micrograph of a defect portion in the porous ceramic thin film after osmotic plating, and it was revealed by EDS analysis that the defect central portion was covered with silver. This defective portion is considered to be formed by peeling off a part of the ceramic porous body.
  • Example 3 In the same manner as in Example 1, palladium was deposited on the defective portion of the ceramic porous thin film (porous ceramic film), and a porous filter in which the defect was closed and / or covered with palladium was produced. After washing this porous filter with water, the outer surface of the porous filter was immersed in a commercially available electroless palladium plating solution at 50 ° C., and the outer surface of the porous filter was plated with palladium. The average film thickness of this palladium thin film was 0.8 ⁇ m.
  • J is the hydrogen permeation flow rate (mmol / s / m 2 )
  • p1 is the inlet-side hydrogen partial pressure (Pa)
  • p2 is the outlet-side hydrogen partial pressure (Pa).
  • J ′ is a gas permeation flow rate (mmol / s / m 2 )
  • p3 is an inlet side gas partial pressure (Pa)
  • p4 is an outlet side gas partial pressure (Pa).
  • a gas permeation test was conducted in the range of a hydrogen differential pressure of 0 to 2 atmospheres and an argon differential pressure of 0 to 4 atmospheres.
  • a hydrogen permeation rate of 0.5 / s / m 2 / Pa 0.5 and an argon permeation rate of 9.5 nmol / s / m 2 / Pa were obtained.
  • the hydrogen selectivity was about 1600.
  • Example 4 Except that the deposition time of palladium was set to 1 hour, the porous material was formed by depositing palladium on the defective part of the porous ceramic thin film (porous ceramic film) in the same manner as in Example 1, and closing and / or covering the defect with palladium. I made a filter. After washing this porous filter with water, the outer surface of the porous filter was immersed in a commercially available electroless palladium plating solution at 50 ° C. to deposit palladium on the outer surface of the porous filter.
  • the inside of the filter (the inside of the bottomed cylindrical sintered metal filter) is pumped to guide the electroless palladium plating solution to the penetration defects remaining in the palladium membrane precursor
  • the pressure was reduced to 0.1 atmosphere by electroless palladium plating.
  • the average film thickness of the obtained palladium thin film was 1.9 ⁇ m.
  • Example 5 A porous ceramic body was prepared in the same manner as in Example 1 except that a commercially available electroless copper plating solution was used instead of the electroless palladium plating solution in Example 1 and the solution was immersed in an aqueous solution having a glucose concentration of 4 mol / l at room temperature for 3 hours. Copper was deposited on the defective portion of the thin film (porous ceramic film), and a porous filter was produced in which the defects were closed and / or covered with copper. This was immersed in a commercially available palladium plating solution containing no reducing agent for 18 hours, and the copper surface was replaced with palladium.
  • a commercially available electroless copper plating solution was used instead of the electroless palladium plating solution in Example 1 and the solution was immersed in an aqueous solution having a glucose concentration of 4 mol / l at room temperature for 3 hours. Copper was deposited on the defective portion of the thin film (porous ceramic film), and a porous filter was produced in which the defects were closed and
  • this porous filter was immersed in the commercially available alkali catalyst at 50 degreeC, the palladium ion was made to adhere to an outer surface, and it reduced in the commercially available reducing solution continuously. Thereafter, a palladium thin film was formed by the same operation as in Example 4. The average film thickness of the formed palladium thin film was 1.6 ⁇ m. Then, the palladium thin film formed on the porous filter is immersed in an electroplating solution made of a copper ethylenediamine complex, and copper electroplating is performed on the palladium thin film while reducing the pressure inside the filter to 0.1 atm with a pump. A copper thin film was formed on the palladium thin film.
  • a hydrogen separation membrane comprising a palladium / copper alloy thin film having a porous filter as a support by heating and heating to 400 ° C. in an argon stream after washing and drying, followed by heat treatment at 400 ° C. in a hydrogen stream for 50 hours.
  • the obtained alloy had an average copper content of 44% by weight, and the alloy had an average film thickness of 3.4 ⁇ m.
  • Example 6 In the same manner as in Example 4, palladium was deposited on the defective part of the ceramic porous thin film (porous ceramic film), and a porous filter in which the defect was closed and / or covered with palladium was manufactured. Thereafter, a palladium thin film was formed by the same operation as in Example 4. The average film thickness of the formed palladium thin film was 0.7 ⁇ m. Then, the palladium thin film formed on the porous filter is immersed in an electroplating solution composed of palladium and silver ammine complexes, and the inside of the filter is reduced to 0.1 atm by a pump while the palladium / silver is deposited on the palladium thin film. The alloy was electroplated to form a palladium / silver alloy thin film on the palladium thin film.
  • a hydrogen separation membrane comprising a palladium / silver alloy thin film with a porous filter as a support by heating to 400 ° C. under an argon stream after washing and drying, followed by heat treatment at 400 ° C. for 50 hours in a hydrogen stream.
  • the obtained alloy had an average silver content of 5% by weight and an average film thickness of 1.7 ⁇ m.
  • Example 7 Except for immersing in an aqueous solution with a glucose concentration of 4 mol / l at room temperature for 5 hours, the same procedure as in Example 1 was carried out to deposit palladium on the defective part of the ceramic porous thin film (porous ceramic film) and close the defect with palladium. And / or coated porous filters were made. This porous filter was immersed in a commercially available alkaline catalyst at 50 ° C. to allow palladium ions to adhere to the outer surface, and subsequently reduced in a commercially available reducing solution. Then, a palladium thin film was formed by the same operation as in Example 4. The average film thickness of the formed palladium thin film was 2.3 ⁇ m.
  • a copper thin film of 0.5 ⁇ m was formed on the palladium thin film by the same operation as in Example 5.
  • a palladium plating solution containing no commercially available reducing agent is filled inside the porous filter on which the metal thin film is formed, and the outer surface thereof is placed in an aqueous solution containing 2 mol / L of glucose containing dimethylaminoborane at room temperature. Soaked for hours. Due to the osmotic pressure, the palladium plating solution containing no reducing agent flowed out to the defective portion of the metal thin film formed on the outer surface of the porous filter, and palladium metal was deposited in the defective portion. Then, this was immersed in a commercially available copper electroless plating solution at room temperature to form a 0.2 ⁇ m copper thin film, and then a copper thin film was formed thereon in the same manner as in Example 5.
  • a hydrogen separation membrane comprising a palladium / copper alloy thin film having a porous filter as a support by heating and heating to 400 ° C. in an argon stream after washing and drying, followed by heat treatment at 400 ° C. in a hydrogen stream for 50 hours.
  • the obtained alloy had an average copper content of 44% by weight and an average film thickness of 4.7 ⁇ m.
  • Comparative Example 1 The ceramic porous thin film (porous ceramic film) of Example 1 was washed with water without clogging defects with a metal, and the ceramic porous thin film was immersed in a commercially available electroless palladium plating solution at 50 ° C. The thin film surface was plated with palladium. The average film thickness of this palladium thin film was 0.8 ⁇ m.

Abstract

Cette invention concerne un procédé de production qui élimine les défauts présents dans une membrane céramique poreuse extrêmement utile comme matière de filtration, de manière à obtenir un filtre poreux à performances de fractionnement élevées. L'invention concerne également une membrane de séparation de l'hydrogène dotée d'une forte sélectivité pour l'hydrogène et d'une forte perméabilité à l'hydrogène, et qui forme une mince pellicule de palladium ou d'alliage de palladium exempte de défauts sur la face supérieure de la membrane céramique poreuse. Une solution de placage métallique située sur une face de la membrane céramique poreuse est transférée sur l'autre face de la membrane céramique poreuse par pression osmotique et le métal se dépose sur les défauts donnant sur la surface de la membrane céramique poreuse de manière à les obturer et/ou à les recouvrir. Une fois ces défauts colmatés, le palladium ou l'alliage de palladium recouvre la membrane céramique poreuse.
PCT/JP2011/056977 2010-03-29 2011-03-23 Filtre poreux, son procédé de production, membrane de séparation de l'hydrogène avec filtre poreux utilisé comme support, procédé de colmatage de défauts et procédé de séparation de l'hydrogène WO2011122414A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102861517A (zh) * 2012-09-19 2013-01-09 常州大学 一种冷轧超薄钯-银合金膜的制备方法
JP2015147208A (ja) * 2014-01-07 2015-08-20 国立研究開発法人産業技術総合研究所 水素分離膜の製造方法
EP4321240A1 (fr) 2022-08-08 2024-02-14 Toyota Jidosha Kabushiki Kaisha Filtre de séparation d'hydrogène

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002064241A1 (fr) * 2001-02-16 2002-08-22 Sumitomo Electric Industries, Ltd. Structure permeable a l'hydrogene et procede de fabrication ou de reparation de cette derniere
JP2004122006A (ja) * 2002-10-03 2004-04-22 National Institute Of Advanced Industrial & Technology 水素分離膜、その製造方法及び水素の分離方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3882567B2 (ja) * 2000-11-24 2007-02-21 住友電気工業株式会社 物質分離構造体
CN1327942C (zh) * 2004-01-09 2007-07-25 中国科学院大连化学物理研究所 一种复合金属钯膜或合金钯膜及其制备方法
JP2006239679A (ja) * 2005-02-04 2006-09-14 Ngk Insulators Ltd 水素分離体及びその製造方法
US7604690B2 (en) * 2005-04-05 2009-10-20 Wostec, Inc. Composite material for ultra thin membranes
US8177890B2 (en) * 2008-06-30 2012-05-15 The Ohio State University Stable supported Pd-alloy membranes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002064241A1 (fr) * 2001-02-16 2002-08-22 Sumitomo Electric Industries, Ltd. Structure permeable a l'hydrogene et procede de fabrication ou de reparation de cette derniere
JP2004122006A (ja) * 2002-10-03 2004-04-22 National Institute Of Advanced Industrial & Technology 水素分離膜、その製造方法及び水素の分離方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102861517A (zh) * 2012-09-19 2013-01-09 常州大学 一种冷轧超薄钯-银合金膜的制备方法
JP2015147208A (ja) * 2014-01-07 2015-08-20 国立研究開発法人産業技術総合研究所 水素分離膜の製造方法
EP4321240A1 (fr) 2022-08-08 2024-02-14 Toyota Jidosha Kabushiki Kaisha Filtre de séparation d'hydrogène

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