WO2016122248A1 - Procédé de placage autocatalytique pour membrane de séparation cylindrique ou tubulaire et appareil de placage correspondant - Google Patents

Procédé de placage autocatalytique pour membrane de séparation cylindrique ou tubulaire et appareil de placage correspondant Download PDF

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Publication number
WO2016122248A1
WO2016122248A1 PCT/KR2016/001001 KR2016001001W WO2016122248A1 WO 2016122248 A1 WO2016122248 A1 WO 2016122248A1 KR 2016001001 W KR2016001001 W KR 2016001001W WO 2016122248 A1 WO2016122248 A1 WO 2016122248A1
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WIPO (PCT)
Prior art keywords
plating
tubular
support
cylindrical
cylindrical support
Prior art date
Application number
PCT/KR2016/001001
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English (en)
Korean (ko)
Inventor
이신근
서범석
Original Assignee
한국에너지기술연구원
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Publication of WO2016122248A1 publication Critical patent/WO2016122248A1/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
    • B01D71/022—Metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • 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
    • B01D69/04—Tubular membranes
    • 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
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/105—Support pretreatment
    • 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
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/108—Inorganic support material
    • 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
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/1213—Laminated layers
    • 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
    • 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
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/16—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/42—Details of membrane preparation apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/50—Control of the membrane preparation process

Definitions

  • the present invention relates to a method for producing a surface plated tubular or cylindrical support, and a plating reactor therefor, and more particularly to electroless separation of a tubular or cylindrical separator in the production of a composite membrane for separating hydrogen from a mixed gas or constructing a membrane reactor. It relates to a plating method and a plating apparatus using the same.
  • Chemical plating is a method of treating a surface of a material with a metal layer by reducing metal ions in an aqueous solution of a metal salt and depositing it on the surface of the material without supplying electricity from the outside. These methods fall into substitutional plating, contact plating, noncatalytic chemical plating and catalytic chemical plating.
  • Substituted plating is a method of immersion plating, in which a metal having a high ionization tendency is immersed in a metal solution having a high ionization tendency, and a metal having a high ionization tendency is deposited on the surface of the material while the material metal is dissolved by a local cell effect.
  • the plating thickness is thin and the adhesion is not well used.
  • zinc substitution plating is used as a plating pretreatment method for aluminum base.
  • Contact plating is a method of forming a battery by contacting a metal to be plated with a metal, and electrodepositing the object to be plated with a negative electrode. It can be used when precipitation of electroless nickel plating is started, but it is not used much. Representative of non-catalyst chemical plating is silver mirror reaction, which is used for electric poles and the like. The surface to be plated must be activated with tin chloride (SnCl 2 ), but some precipitate even where it is not activated.
  • SnCl 2 tin chloride
  • Catalytic chemical plating is the electroless plating that is now commonly practiced. Precipitating a metal having a catalytic action on the surface of the material is used as a nucleus, and metal is continuously deposited thereon, which is advantageous for selectively plating only a part.
  • Electroless plating is a method in which a metal plating layer can be spontaneously formed on a surface by using a reducing agent, and metal ions are reduced and precipitated to form metal plating layers by accepting electrons emitted when the reducing agent in the solution is oxidized.
  • the mechanism by which the plating layer is formed on the surface can be represented by the following reaction formula.
  • R is a reducing agent
  • OX is an oxide of the reducing agent
  • M 2+ is a metal ion
  • M 0 is a reduced metal
  • the electroless plating method can be applied to various metals such as copper, nickel, cobalt and palladium.
  • the advantage of this method is that no special equipment such as power supply and power supply is required.
  • the shape of the plating material is complicated, it is possible to form the plating layer with a uniform thickness and to form a film having excellent corrosion resistance and abrasion resistance.
  • the plating solution is difficult to manufacture, the plating solution is easily decomposed, requires attention to the plating solution management, and has a disadvantage in that the plating speed is slow.
  • Electroless plating has various uses, and is widely used in various mechanical parts such as electric and electronic parts, automotive exterior parts, petroleum industry, food industry equipment, and self-food.
  • hydrogen separator plating may be exemplified.
  • Hydrogen separation membrane is divided into molecular permeable membrane, atomic permeable membrane, electron or proton permeable membrane according to permeation mechanism.
  • the atomic permeable membrane is a metal dense membrane that adsorbs hydrogen molecules on the metal surface, dissociates them into hydrogen atoms, moves between metal lattice, recombines with hydrogen molecules on the opposite side of the separator, and desorbs from the metal surface. Is transmitted.
  • Metals used as hydrogen separation membranes are classified into Ti, V, Nb, Ta, and palladium based groups of Groups IV and V. Among them, membranes using palladium or palladium alloys have high hydrogen permeability and chemical stability, and thus are widely used in hydrogen purification processes. It is being used, and also shows its applicability to various industrial processes.
  • the supports used for the palladium-based composite membranes are porous stainless steel, porous glass, and porous ceramics.
  • methods for preparing palladium-based composite membranes include sputtering, chemical vapor deposition (CVD), electrolytic plating, electroless plating, and spray pyrolysis ( spray pyrolysis) is used.
  • the surface of the support is not in the form of a flat plate, so that the support may be compared to methods such as sputtering, chemical vapor deposition (CVD) and spray pyrolysis.
  • Chemical plating such as electroless plating in which a metal layer is formed by chemical reaction by immersion in a plating solution, is economical and easy to manufacture.
  • a first step of preparing a plating reactor provided; And a second step of plating in a state in which the rotating shaft and the plating surface are in parallel while rotating the tubular or cylindrical support by rotating the tubular or cylindrical support on the longitudinal central axis of the tubular or cylindrical support in the plating vessel filled with a plating solution.
  • a method for producing a phosphorus surface plated tubular or cylindrical support is provided.
  • the second aspect of the present invention is a plating reactor containing a plating liquid having a cross-sectional shape concentric with the vertical cross section of the support with respect to the longitudinal central axis of the tubular or cylindrical support. Vessel; And a support rotating motor for rotating the longitudinal central axis of the tubular or cylindrical support in the rotational axis, wherein the tubular or cylindrical support is rotated and the plating solution is vortexed while the plating solution is plated in parallel with the rotational axis.
  • a method of manufacturing a tubular or cylindrical hydrogen separation membrane the plating reactor having a plating container having a cross-sectional shape concentric with the vertical cross section of the support based on the longitudinal central axis of the tubular or cylindrical porous support.
  • a method of manufacturing a surface-plated tubular or cylindrical support the plating vessel containing a plating solution; And a first step of preparing a plating reactor having a gas droplet injector installed below the plating vessel and injecting a gas bubble in a manner of forming turbulence in the plating liquid. And forming a gas bubble turbulence at the bottom of the plating vessel during plating of the tubular or cylindrical support, so that the gas bubble turbulence moves upward by buoyancy, without the metal concentration gradient depending on the distance from the support surface and without the metal concentration gradient between the upper and lower portions of the plating liquid. And a second step of mixing the plating solution so that the metal concentration is uniform and removing a gas generated during the plating reaction on the support surface from the support surface.
  • a plating reactor for plating a tubular or cylindrical support surface, the plating vessel containing a plating liquid in a form capable of accommodating a tubular or cylindrical support; And a gas droplet injector installed under the plating vessel to inject gas bubbles in a manner of forming turbulence in the plating liquid, wherein the gas bubbles injected into the turbulence move upward by buoyancy and according to a distance from the support surface.
  • Plating reactor characterized in that the plating liquid is mixed so that the metal concentration of the plating liquid is uniform without the concentration gradient and the metal concentration gradient between the upper and lower portions of the plating liquid, and the gas generated during the plating reaction on the support surface is removed from the support surface to improve the plating efficiency.
  • a plating layer is formed on a surface of a support by placing a support in a reactor filled with a plating liquid to induce a plating reaction such as a metal reduction reaction by contacting a plating component on a surface of the support.
  • the process is carried out.
  • bubbles are generated due to a gas such as nitrogen (N 2 ) gas, and these bubbles may form pores in the plating layer or stay in the plating layer for a certain time to hinder the plating reaction itself, resulting in deterioration of plating quality. .
  • a concentration gradient of the plating component may occur in the reactor, and thus the efficiency of the plating reaction may decrease with time, and the efficiency of the plating reaction may also be reduced by exothermic or endothermic due to the plating reaction.
  • the rotating shaft and the plated surface is vortexed by rotating the tubular or cylindrical support by rotating the tubular or cylindrical support around the longitudinal central axis of the tubular or cylindrical support. It has been found that plating in parallel can improve plating quality and make the plating reaction more efficient.
  • the gas bubble turbulence is moved upward by buoyancy, so that the metal between the upper and lower portions of the plating liquid without the gradient of metal concentration according to the distance from the surface of the support.
  • the plating liquid can be improved and the plating reaction can be performed more efficiently by mixing the plating liquid so that the metal concentration of the plating liquid is uniform without concentration gradient, and removing the gas generated during the plating reaction on the support surface from the support surface. .
  • the present invention is based on this.
  • Plating vessel to accommodate the plating solution; And a first step of preparing a plating reactor having a gas droplet injector installed below the plating vessel and injecting a gas bubble in a manner of forming turbulence in the plating liquid.
  • the plating liquid is mixed so that the metal concentration of the plating liquid is uniform without the metal concentration gradient according to the distance from the support surface and without the metal concentration gradient between the upper and lower portions of the plating liquid, and occurs during the plating reaction on the surface of the support. And a second step of removing the gas from the support surface.
  • the gas formed by the plating reaction (for example, nitrogen gas) forms pores in the plating coating layer or inhibits plating, but in the present invention, as described above, by rotating and plating the support to be plated, and / or a gas formed under the plating vessel
  • the drop turbulence is moved upward by buoyancy, thereby allowing the gases to desorb well from the plating surface to solve the above problem.
  • the plating reactor is provided with a temperature control jacket on the outer surface of the plating vessel, if the plating reaction is an exothermic reaction, the refrigerant in the temperature control jacket flows, if the plating reaction is an endothermic reaction, the fruit in the temperature control jacket flows It may be there.
  • the Pd or Pd alloy after performing the electroless plating in the production of the hydrogen separation membrane, it may be heat-treated in a hydrogen-containing gas atmosphere at a temperature of 450-550 °C for 1 to 20 hours.
  • the support rotating motor 20 is rotated in the plating container 10 filled with a plating solution as shown in FIG. 2.
  • the tubular or cylindrical support 1 is rotated around the longitudinal center axis of the tubular or cylindrical support 1, the tubular or cylindrical support 1 is rotated and is vortexed to form a plating solution while the plating axis is plated in parallel with the rotation axis and the plating surface.
  • the separation of generated bubbles is facilitated and the concentration gradient inside the plating vessel is not only minimized, and heat dissipation is facilitated, thereby improving plating quality and performing plating reaction more efficiently.
  • a predetermined amount is filled in the plating vessel in accordance with the length of the support to be plated with a plating solution mixed with a reducing agent in an appropriate ratio.
  • the separator is detached from the support rotating motor and dried.
  • the present invention is to rotate the tubular or cylindrical support on the longitudinal center axis of the tubular or cylindrical support in the plating vessel filled with a plating liquid to vortex the plating solution while the plating liquid is vortexed and / or plated in parallel with the plating plane and / or under the plating vessel.
  • FIG. 1 is a schematic view schematically showing the structure of a plating reactor according to an aspect of the present invention from the front (a) and side (b).
  • FIG. 2 is a schematic view schematically showing an enlarged support rotating motor, support and plating vessel in the plating reactor of FIG.
  • FIG 3 is a schematic view schematically showing the structure of a plating reactor according to another embodiment of the present invention from the front (a) and side (b).
  • FIG. 5 is a cross-sectional view of the vortex formation when the support rotating motor rotates in the plating reactor of FIG. 3.
  • FIG. 6 is a schematic diagram schematically showing a plating reactor fabricated to be mounted on a hood in which a large-capacity vent facility is installed according to an aspect of the present invention.
  • FIG. 7 is a schematic view showing a plating reactor equipped with an independent vent facility according to an aspect of the present invention.
  • Figure 8 shows the appearance of the separator prepared according to Example 2.
  • FIG. 9 is a schematic diagram in which a gas bubble injector is further installed below the plating vessel in the plating reactor of FIG. 2.
  • Figure 11 shows the appearance of the separator prepared according to Example 3.
  • tubular or cylindrical support 10 plating vessel
  • thermostatic jacket 50 thermostatic fluid supply port
  • Vortex rod 90 Vortex rod holder
  • a plating reactor according to an embodiment of the present invention was manufactured.
  • Example 2 Palladium Plating of Tubular Separators Using Plating Reactor of the Present Invention
  • Palladium plating was performed on the tubular separator using the plating reactor of the present invention according to FIG.
  • the ceramic support prepared in the motor for moving the support up and down was mounted.
  • a predetermined amount was filled in the plating vessel in accordance with the length of the support to be plated with a plating solution mixed with a reducing agent in an appropriate ratio.
  • the plating solution used is shown in Table 1 below.
  • the process of supplying the temperature control fluid to the temperature control fluid supply port and collecting the fluid to the temperature control fluid outlet so as to maintain a constant temperature according to the situation was adjusted to 20 ° C.
  • the support was inserted into the plating vessel by using the motor for the support shaft.
  • the plating reaction was performed while rotating the support at 300 RPM using a support motor.
  • the separator was detached from the support rotating motor and dried to prepare a separator plated with palladium.
  • the prepared membrane was 1/4 inch in diameter, 17cm long.
  • the white portion is a palladium plated portion and the palladium plating quality is excellent.
  • Example 3 Palladium Plating of Tubular Membrane Using Plating Reactor of the Present Invention

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Combustion & Propulsion (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Electrochemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Chemically Coating (AREA)

Abstract

La présente invention concerne un procédé destiné à produire un support tubulaire ou cylindrique plaqué en surface et un réacteur de placage correspondant. Un réacteur de placage selon la présente invention met en rotation, dans un bain de placage rempli d'une solution de placage, un support tubulaire ou cylindrique dont l'axe longitudinal est l'axe de rotation, et plaque le support tubulaire ou cylindrique, l'axe de rotation étant parallèle à la surface de placage, tout en créant des tourbillons dans la solution de placage, ce qui permet d'améliorer la qualité du placage sur la surface du support tubulaire ou cylindrique et permet de réaliser la réaction de placage de façon plus efficace. De plus, le réacteur de placage selon la présente invention est pourvu d'un injecteur de bulles de gaz, sous le bain de placage, destiné à injecter des bulles de gaz par création d'une turbulence dans la solution de placage, de sorte que, à mesure que les bulles de gaz créées par la turbulence se déplacent vers le haut sous l'effet de la flottabilité, la solution de placage est mélangée, de telle sorte que la concentration en métal de la solution de placage est uniforme, sans gradient de concentration de métal dû à la distance par rapport à la surface du support ni gradient de concentration du métal entre la partie supérieure et la partie inférieure de la solution de placage, et le gaz généré sur la surface du support pendant la réaction de placage est éliminé de celle-ci, ce qui permet d'améliorer l'efficacité du placage.
PCT/KR2016/001001 2015-01-29 2016-01-29 Procédé de placage autocatalytique pour membrane de séparation cylindrique ou tubulaire et appareil de placage correspondant WO2016122248A1 (fr)

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KR102102992B1 (ko) * 2018-09-04 2020-04-22 한국에너지기술연구원 세라믹 파우더 유동화를 이용한 도금방법
KR102582678B1 (ko) * 2021-06-30 2023-09-25 주식회사 하이젠에너지 도금속도측정이 가능한 무전해 도금장치

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KR20100129123A (ko) * 2009-05-29 2010-12-08 경기대학교 산학협력단 팔라듐 합금 수소 분리막의 제조방법
KR20140101334A (ko) * 2011-11-16 2014-08-19 쉘 인터내셔날 리써취 마트샤피지 비.브이. 누출 안정성 기체 분리 막 시스템의 제조 또는 재상태조정 방법
KR20140120592A (ko) * 2013-04-03 2014-10-14 한국에너지기술연구원 수소 분리막용 멤브레인 및 이의 이용
KR20140123218A (ko) * 2013-04-12 2014-10-22 삼성전자주식회사 수소 분리막 및 상기 수소 분리막을 포함하는 수소 분리 장치

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