KR20130041415A - Hydrogen filtering membrane having pipe-shaped structure and manufacturing method of the same - Google Patents

Abstract

PURPOSE: A tubular hydrogen separation membrane module and a manufacturing method thereof are provided to comprise a metal film having a hydrogen transfer film and a metal film having the characteristics of hydrogen separation and transfer to improve the characteristic of hydrogen separation and to separate high purity hydrogen from a mixed gas containing hydrogen. CONSTITUTION: A tubular hydrogen separation membrane module includes a tubular support(110) having a porous ceramic material; a hydrogen transfer film(130) of a ceramic material of a ceramic material and a metal film(140). A tube(120) providing a path discharging hydrogen gas is formed inside the tubular support. The nano-sized pores are formed on the hydrogen transfer film, whereby the hydrogen transfer film has the characteristic of transferring hydrogen to the tubular support. The metal layer is formed on the outside of the hydrogen transfer film and has the characteristics of hydrogen separation and transfer, thereby separating hydrogen from a mixed gas containing hydrogen and discharging the separated hydrogen to the hydrogen transfer film. The average pore size of the hydrogen transfer film is 0.01-1Mm. The porosity of the hydrogen transfer film is 0.1-0.2 which is smaller than the porosity of the tubular support. The hydrogen transfer film is composed of a film denser than the tubular support. The porosity of the metal layer is smaller than the porosity of the hydrogen transfer film. The metal layer comprises a film denser than the hydrogen transfer film.

Description

Hydrogen filtering membrane having pipe-shaped structure and manufacturing method of the same

The present invention relates to a tubular hydrogen separation membrane module and a method of manufacturing the same, and more particularly, a hydrogen transfer membrane is coated (or deposited) on a porous tubular support, and a metal membrane having hydrogen separation and transfer characteristics is the hydrogen transfer. The present invention relates to a hydrogen separation membrane module having a hydrogen separation characteristic improved by coating (or depositing) on a membrane and a method of manufacturing the same.

Hydrogen energy is in the spotlight as an alternative energy source that can solve the problem of depletion and pollution of fossil fuels such as oil and coal. Techniques for producing hydrogen molecules include various methods such as electrolysis of water, biochemical reaction by microorganisms, filtration of natural hydrogen molecules, and production using high temperature heat.

However, most of the methods are difficult to secure hydrogen as an energy source due to cost and the like, and thus, active researches have been conducted to separate high-purity hydrogen molecules by filtration from low-purity or waste hydrogen-containing gases. .

As a method for separating hydrogen mixed with nitrogen, oxygen, carbon dioxide, carbon monoxide, etc., there have been attempts to separate using a membrane having a nanometer (pores) sized pores. However, to date, it is difficult to manufacture a hydrogen separation membrane having a uniform pore structure, and thus it has not been reached until the step of obtaining high purity hydrogen.

As a method for obtaining high purity hydrogen, a technique for separating and purifying pure hydrogen only at a high temperature has been studied. Representative hydrogen separator material is a material of a perovskite structure having a composition of ABO ₃ . The most studied composition was SrCeO ₃ , BaCeO ₃ The durability is excellent while the separation characteristics are low. According to a recent study (Korean Patent Registration No. 10-0691645), BaCe _x YM _{1 - x} O ₃ and LaSr _x M _{1 - x} O ₃ (M = La, Y, Yb, Ga, Gd) to improve hydrogen separation characteristics , In, Ge), and the like are being studied. Metal nanoparticles such as Ni, Pt, Rh, and Pd are added thereto to prepare ceramic-metal nanocomposites to further improve hydrogen separation characteristics.

However, the improvement of the hydrogen separation characteristics of the material does not completely solve the method for producing high purity hydrogen. As studied in Korean Patent Registration No. 10-0691645, an oxide that is a raw material is usually mixed in a required ratio, and then sintered into a plate shape at a high temperature of 1400 ° C. or above, and the separator is polished into a flat plate.

Hydrogen separation characteristics tend to increase rapidly as the thickness becomes thinner. However, the thickness of the hydrogen separation membrane body is limited to a thickness that does not break during the polishing process. In general, the limit of grinding is about 0.1 mm level, and if you want to obtain a lower thickness than this problem is frequently caused by breakage. Therefore, although the ion conductivity of the separator material is improved by the conventional technology, the use of the separator itself by grinding the separator in a flat plate has many limitations in order to achieve the purpose of hydrogen separation.

Accordingly, the inventors of the present application developed a patent and applied for a tubular hydrogen separation membrane body, and received a patent registration (Korean Patent Publication No. 10-0966249).

Republic of Korea Patent Publication No. 10-0966249 Republic of Korea Patent Publication No. 10-2011-0047498

The problem to be solved by the present invention is formed by coating (or depositing) a hydrogen transfer film on a porous tubular support, and a hydrogen separation property by coating (or depositing) a metal film having hydrogen separation and transfer properties on the hydrogen transfer film. The improved hydrogen separation membrane module and its manufacturing method are provided.

The present invention is a ceramic material having a characteristic that delivers hydrogen to the tubular support formed with a tubular support formed of a ceramic material having a porous inside and a nano-sized pores formed therein to provide a passage through which hydrogen gas is discharged. And a metal film formed on the outside of the hydrogen transfer film and having a hydrogen separation and transfer property to separate hydrogen from a mixed gas containing hydrogen and discharge the hydrogen into the hydrogen transfer film, wherein the hydrogen transfer film has an average pore. Its size is 0.01∼1㎛ and porosity is 0.1∼0.2, which is smaller than the porosity of the tubular support and is denser than the tubular support, and the metal membrane has a porosity smaller than the porosity of the hydrogen transfer membrane and is dense than the hydrogen transfer membrane. It provides a tubular hydrogen separation membrane module consisting of.

The metal film may be formed of a palladium (Pd) metal having a higher melting point than 300 to 900 ° C. at which the hydrogen separation membrane module is used.

The metal film is selected from palladium (Pd) metal having a higher melting point than 300 to 900 ° C. at which the hydrogen separation membrane module is used, and cobalt (Co), nickel (Ni), and copper (Cu) having a melting point lower than that of palladium (Pd). At least one metal may be alloyed with a palladium (Pd) -based alloy, and the at least one metal selected from cobalt (Co), nickel (Ni), and copper (Cu) may include palladium (Pd) in the palladium (Pd) -based alloy. It is preferable to contain 1-80 weight part with respect to 100 weight part of metals.

The hydrogen transfer membrane is a silicon carbide (SiC), alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ), yttria stabilized zirconia (yttria It may be made of at least one ceramic material selected from stabilized zirconia) and aluminum titanate (AlTiO ₃ ).

The tubular support is silicon carbide (SiC), alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ), yttria stabilized zirconia (yttria-) which does not occur deformation at the temperature of the hydrogen separation membrane module 300 ~ 900 ℃ It may be made of at least one ceramic material selected from stabilized zirconia) and aluminum titanate (AlTiO ₃ ), the average pore size of the tubular support is 0.1 ~ 100㎛ and porosity is preferably 0.2 ~ 0.4.

In addition, the present invention, the step of mixing and kneading the raw material, pore-forming agent and solvent made of a ceramic material that does not occur deformation at the temperature at which the hydrogen separation membrane module is used, and a tube providing a passage through which hydrogen gas is discharged through the kneaded result Forming and firing to be provided therein to form a tubular support made of a porous ceramic material, and sealing the tube inside the tubular support not to be exposed, and nano-sized pores are formed to transfer hydrogen to the tubular support Forming a hydrogen transfer film made of ceramic material on the tubular support, sealing the tube inside the tubular support so as not to be exposed, and separating hydrogen from a mixed gas containing hydrogen by having a hydrogen separation and transfer characteristic; Forming a metal film discharged to the hydrogen transfer film on the outside of the hydrogen transfer film And heat-treating the resultant metal film formed thereon, wherein the hydrogen transfer film has an average pore size of 0.01 to 1 μm and a porosity of 0.1 to 0.2, which is smaller than the porosity of the tubular support and is formed into a denser film than the tubular support. The metal membrane provides a method of manufacturing a tubular hydrogen separation membrane module in which the porosity is smaller than the porosity of the hydrogen transfer membrane and formed into a denser membrane than the hydrogen transfer membrane.

The metal film may be formed of a palladium (Pd) metal having a higher melting point than 300 to 900 ° C. at which the hydrogen separation membrane module is used.

The metal film is selected from palladium (Pd) metal having a higher melting point than 300 to 900 ° C. at which the hydrogen separation membrane module is used, and cobalt (Co), nickel (Ni), and copper (Cu) having a melting point lower than that of palladium (Pd). At least one metal may be formed of an alloyed palladium (Pd) -based alloy, and the at least one metal selected from cobalt (Co), nickel (Ni), and copper (Cu) may be formed of palladium (Pd) -based alloy. Pd) It is preferable to contain 1-80 weight part with respect to 100 weight part of metals.

The forming of the metal film on the outer side of the hydrogen transfer film may include a deposition chamber, a tubular support having the hydrogen transfer film disposed in the deposition chamber, and a palladium to be deposited on the surface of the hydrogen transfer film. Pd) a first target for supplying metal, and a cobalt (Co), nickel (Ni), copper (Cu) or an alloy thereof to be disposed in the deposition chamber and to be deposited onto the surface of the hydrogen transfer film. A second target, a first power supply for supplying a voltage to the first target, a second power supply for supplying a voltage to the second target, and a gas for supplying a gas for plasma formation in the deposition chamber Preparing a deposition apparatus including a supply means, the hydrogen transfer film is formed in conjunction with the rotation of the holder on which the tubular support on which the hydrogen transfer film is formed The shaped support may be formed by the metal film is to be rotated.

The metal film may be formed by revolving the tubular support on which the hydrogen transfer film is formed in association with rotation of a holder support for supporting the holder at regular intervals.

The first target and the second target are at an angle θ in the range of 90 ° <θ <180 ° with respect to the tubular support on which the hydrogen transfer film is formed so that the flux of the material to be deposited reaches the hydrogen transfer film evenly. And the tubular support on which the hydrogen transfer film is formed is positioned in an overlapping region in which a flux of particles sputtered from the first target and a region of flux of particles sputtered from the second target overlap each other. A film can be formed.

As the heating means for controlling the temperature of the tubular support on which the hydrogen transfer film is formed, the temperature of the tubular support on which the hydrogen transfer film is formed may be kept constant in the range of 300 to 600 ° C. to form the metal film.

The hydrogen transfer membrane is a silicon carbide (SiC), alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ), yttria stabilized zirconia (yttria It may be formed of at least one ceramic material selected from stabilized zirconia) and aluminum titanate (AlTiO ₃ ).

Forming the hydrogen transfer film on the tubular support, the step of installing the tubular support in cooperation with the rotatable holder provided in the deposition chamber, maintaining the inside of the deposition chamber at a constant pressure, flow control means The carrier gas is selected from silicon carbide (SiC), alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ), yttria-stabilized zirconia and aluminum titanate (AlTiO ₃ ). Aerosolizing the raw material powder by supplying at least one ceramic powder into a space; supplying the formed aerosol to a nozzle in the deposition chamber by a pressure difference; and between the nozzle of the nozzle and the tubular support to be deposited. Allowing aerosol to be sprayed toward the tubular support while keeping the distance constant within the range of 2-20 mm The aerosol sprayed on the tubular support may be formed while being pulverized by the impact to form a hydrogen transfer film.

The tubular support is silicon carbide (SiC), alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ), yttria stabilized zirconia (yttria-) which does not occur deformation at the temperature of the hydrogen separation membrane module 300 ~ 900 ℃ It may be formed of at least one ceramic material selected from stabilized zirconia) and aluminum titanate (AlTiO ₃ ), a plurality of pores are formed in the tubular support through the firing, the average pore size of the tubular support is 0.1 ~ 100 It is preferable that it is micrometer and porosity is 0.2-0.4.

According to the tubular hydrogen separation membrane module according to the present invention, a hydrogen transfer membrane is formed (coated or deposited) on a porous tubular support, and a metal film having hydrogen separation and transfer characteristics is coated (or deposited) on the hydrogen transfer membrane. This improves the hydrogen separation characteristics.

High purity hydrogen can be separated from the mixed gas containing hydrogen using the tubular hydrogen separation membrane module according to the present invention.

In addition, according to the present invention, it is possible to recycle the mixed gas containing hydrogen discarded in industrial sites, etc., there is an advantage that can save resources.

1 is a view schematically showing a tubular hydrogen separation membrane module according to a preferred embodiment of the present invention.
2 is a view schematically showing an aerosol film formation apparatus.
FIG. 3 is a view schematically illustrating a case in which the tubular support is rotated and linearly moved, and an aerosol is sprayed from the nozzle to form a film.
FIG. 4 is a view schematically illustrating a case in which an aerosol is sprayed and formed as the tubular support is rotated and the nozzle is linearly moved.
5 is a conceptual diagram schematically illustrating a sputter deposition apparatus for forming a metal film.
6 is a view schematically showing the flux of particles emitted from the target of the deposition apparatus.
7 and 8 are views illustrating an appearance of a deposition apparatus according to an example.
9 is a photograph showing a hydrogen separation membrane module prepared according to the experimental example.
10 is a scanning electron microscope (SEM) photograph showing a cross section of a hydrogen separation membrane module manufactured according to the experimental example.
FIG. 11 is a scanning electron microscope (SEM) photograph of the surface of the metal film prepared according to the experimental example before sputter deposition and heat treatment.
12 is a scanning electron microscope (SEM) photograph of the surface of the metal film prepared according to the experimental example after sputter deposition and heat treatment.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the following embodiments are provided to those skilled in the art to fully understand the present invention, and may be modified in various forms, and the scope of the present invention is limited to the embodiments described below. It doesn't happen. Wherein like reference numerals refer to like elements throughout.

The present invention is formed by coating (or depositing) a hydrogen transfer film on a porous tubular support, and a hydrogen separation film having improved hydrogen separation properties by coating (or depositing) a metal film having hydrogen separation and transfer properties on the hydrogen transfer film. Present the module. In addition, the present invention provides a structure for improving the characteristics of the hydrogen separation membrane module. The hydrogen separation membrane module is composed of a metal membrane responsible for hydrogen separation and transfer, a hydrogen transfer membrane serving to transfer hydrogen, and a tubular support supporting the same. Hereinafter, nano-size means a nanometer (nm) size, it is used to mean a size in the range of 1 ~ 1000nm. In addition, hereinafter, the inner side means the direction toward the tube center of the tubular support, the outer side means the direction toward the outside from the tube center of the tubular support.

1 is a view schematically showing a tubular hydrogen separation membrane module according to a preferred embodiment of the present invention.

Referring to FIG. 1, the hydrogen separation membrane module has a tubular support formed therein and provides a porous ceramic material, and a porous nano-sized pores are formed therein, and fine nano-sized pores are formed to supply hydrogen to the tubular support. Hydrogen transfer film made of a ceramic material having a transfer property, and a metal film formed on the outside of the hydrogen transfer film and having a hydrogen separation and transfer characteristics to separate the hydrogen from the mixed gas containing hydrogen and discharged to the hydrogen transfer film . The hydrogen transfer membrane has an average pore size of 0.01 to 1 μm and a porosity of 0.1 to 0.2, which is smaller than that of the tubular support and is dense than the tubular support, and the metal membrane has a porosity smaller than that of the hydrogen transfer membrane. It is made of a finer film than a hydrogen transfer film.

The tube 120 inside the tubular support 110 serves as a passage through which the hydrogen separated by the metal film 140 is discharged from the external mixed gas, and the diameter of the tube 120 is the amount of hydrogen gas separated and discharged. It is determined in consideration of, preferably about 0.5 ~ 10cm.

The size of the tubular support 110 may vary depending on needs, but the pores should be well developed to facilitate the flow of hydrogen gas into the tubular support 110. The tubular support 110 is formed with a number of pores of 0.1 ~ 100㎛ size. Since the hydrogen gas separated by the metal film 140 should be collected into the tube 120 inside the tubular support 110, the pores formed in the tubular support 110 preferably include open pores. That is, it preferably includes pores that open from the tube 120 of the tubular support 110 to the outer surface of the tubular support 110. The size of the pores formed in the tubular support 110 is suitably 0.1 to 100 µm, more preferably 0.5 to 10 µm. If the size of the pores is excessively large, the strength of the tubular support 110 may be insufficient to cause problems during use as a hydrogen separation membrane module, and if the size of the pores is too small, the flow of gas may not be smooth. In addition, the porosity of the tubular support 110 is appropriately 0.2 to 0.4. If the porosity (volume ratio of the pores) of the tubular support 110 is too large, there is a risk of breakage due to the strength decrease, and if the porosity is too small, the flow of gas may not be smooth.

The tubular support 110 can be made in a variety of ways. Silicon carbide (SiC), alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ), yttria-stabilized zirconia in order not to cause deformation at the temperature at which the hydrogen separation membrane module is used And it can be made of a ceramic material such as aluminum titanate (AlTiO ₃ ), the size of the pores by controlling the amount of the pore forming agent (pore forming agent) added to the material of the ceramic material and the raw material particle size of the ceramic material, etc. I can regulate it.

Pore-forming agents, such as organic materials such as tar and carboxymethyl cellulose (CMC), are included in a ceramic material to form a large number of pores in the tubular support 110 through a firing process. There is thermal contraction by the firing process, and the pore-forming agent forms many pores in this predetermined process. The pore-forming agent is burned away at a predetermined temperature (eg, 300 ° C. to 600 ° C.) or more in the firing process, and pores are formed at the burned out site.

The method of forming the tubular support 110 will be described in detail, and the above-described raw material powder of ceramic material is mixed alone or two or more, and kneading is performed by adding a pore-forming agent and a solvent. In consideration of the pore size of the tubular support 110, the average particle size of the ceramic material is preferably about 1 to 50 μm. Water or alcohol may be used as the solvent.

The tube 120 is formed inside the tubular support 110 by molding using extrusion or slip casting. It is preferable to shape | mold so that solid content using an extrusion method may be in the range of 70 to 85%, and when using the slip casting method, it is preferable to shape | mold so that solid content may be in the range of 30 to 60%. Extrusion, slip casting, etc. may be used to make the pipe 120, but may be manufactured in various ways according to desired conditions.

When the tube 120 is formed inside the tubular support 110, it is baked at a temperature of 1200 to 1800 ° C. to produce a final tubular support 110. As described above, the pore-forming agent is burned away at a predetermined temperature (eg, 300 ° C. to 600 ° C.) or more in the firing process, and pores are formed at the burned-out place, and the tubular support 110 is porous. .

Fine nano-sized pores are formed on the outer circumferential surface of the tubular support 110 to form a hydrogen transfer film 120 of a ceramic material having a property of transferring hydrogen to the tubular support. The hydrogen transfer membrane 130 is made of a membrane smaller than the porosity of the tubular support 110 and denser than the tubular support 110. The pore size of the hydrogen transfer membrane 130 having fine pores formed on the tubular support 110 is appropriately 0.01 to 1 μm, more preferably 0.01 to 0.1 μm. If the size of the pores is large, it is not possible to obtain a dense metal film 140 that is highly likely to cause defects in the metal film 140 to be coated on the hydrogen transfer film 130. The porosity of the hydrogen transfer film 130 is preferably 0.1 to 0.2, preferably 0.15 to 0.2. If the porosity is too small, the hydrogen transmittance of the hydrogen transfer film 130 is bad, and if too high, there is a risk of mechanical breakage. Since the hydrogen gas separated by the metal film 140 must be permeated, the pores formed in the hydrogen transfer film 130 preferably include open pores. That is, it is preferable to include pores open from one surface of the hydrogen transfer film 130 to the opposite surface. The thickness of the hydrogen transfer film 130 is suitably 3 to 500 µm, and more preferably 5 to 50 µm.

An aerosol deopsition may be used as a method of forming the hydrogen transfer layer 130 on the tubular support 110. The hydrogen transfer film 130 may be formed on the tubular support 110 by coating (or depositing) the aerosol film formation method using the aerosol film formation apparatus illustrated in FIG. 2.

Referring to FIG. 2, in the aerosol deposition, the aerosol 14 generated from the aerosol supply unit 10 is transferred to a deposition chamber 20 in a low vacuum state together with a carrier gas. It is a process of film-forming, solidified by an impact to the board | substrate (tubular support 110) which is accelerated by the nozzle 22 and is fixed to the holder 24. The aerosol 14 is accelerated at high speed in the pressure-reducing film formation chamber 20 to impinge on the tubular support 110 with high kinetic energy, and the density is increased when particles collide with high kinetic energy due to acceleration, thereby packing at a high density. The growth of the membrane occurs.

Hereinafter, a method of forming the hydrogen transfer film 130 on the tubular support using the aerosol film deposition apparatus shown in FIG. 2 will be described.

First, ceramic powders such as silicon carbide (SiC), alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ), yttria-stabilized zirconia and aluminum titanate (AlTiO ₃ ), which are raw powders, are used. The raw material powder is prepared and attached to the aerosol supply unit 10. In consideration of the pore size of the hydrogen transfer film 130, the average particle size of the ceramic raw material powder is preferably about 5nm ~ 5㎛. When the size of the raw powder particles is less than 5nm, the impact energy is small and difficult to form a film, and when the size exceeds 5㎛, the effect of delivering hydrogen to the tubular support 110 may be small.

The vibrator 18 vibrates the raw material powder 12 so that aggregation between the raw material powder 12 particles is suppressed and can be easily suspended. The rotation speed of the vibrator 18 may be about 100 ~ 300rpm.

The carrier gas is supplied to the aerosol supply unit 10 from the carrier gas supply unit 30. The flow rate of the carrier gas is controlled through the flow control means (MFC) 32, the carrier gas is supplied to the aerosol supply unit 10 through the conduit 34 to float the raw material powder 12. The carrier gas may be air, oxygen (O ₂ ) gas, nitrogen (N ₂ ) gas, argon (Ar) gas, helium (He) gas, or a mixture thereof. The flow rate of the carrier gas supplied from the carrier gas supply part 30 becomes an important factor in the film formation state, thickness, density, porosity, etc. of the raw material powder 12 deposited on the tubular support 110. The flow rate of the carrier gas may vary depending on the particle size of the raw material powder 12, the type of the raw material powder 12, etc., but is generally about 250 to 10,000 sccm per unit area (mm 2) of the nozzle injection port, more preferably. Should be 250 to 2500 sccm per unit area (mm2) of nozzle nozzle. If the flow rate of the carrier gas is less than 250sccm per unit area of the nozzle nozzle (mm2), the density is low and the binding force between particles is weak and can be easily broken.If the flow rate of the nozzle is greater than 10,000sccm per unit area of the nozzle nozzle (mm2) Although a highly dense film is formed by the injection of a strong aerosol, it is difficult to obtain a hydrogen transfer film of uniform thickness.

The raw material powder 12 suspended by the vibrator 18 and the carrier gas forms the aerosol 14. The formed aerosol 14 is supplied from the aerosol supply 10 to the nozzle 22 in the deposition chamber 20 through the conduit 16 by the pressure difference.

Before the aerosol 14 is supplied to the nozzle 22, the inside of the film forming chamber 20 is decompressed by a pressure control unit 40 at a vacuum of a predetermined pressure (for example, about 0.1 to 1 torr), and the film forming chamber at the time of film forming. (20) The internal pressure is preferably maintained at a vacuum degree of a constant pressure (for example, about 1 to 760 torr).

When the pressure in the deposition chamber 20 is set to a desired pressure (vacuum degree) condition, the aerosol 14 is supplied from the aerosol supply unit 10 to the nozzle 22 of the deposition chamber 20 and sprayed toward the tubular support 110. To be. The aerosol 14 sprayed on the tubular support 110 is solidified by the impact to form a hydrogen transfer film 130. It is preferable that the distance between the injection port of the nozzle 22 and the tubular support 110 is about 2-20 mm. If the distance between the nozzle 22 of the nozzle 22 and the tubular support 110 is less than 2 mm, it is difficult to form a uniform film due to the impact energy of the aerosol which is too strong. If the distance exceeds 20 mm, the density is low. The hydrogen transfer layer 130 may be formed.

Since the nozzle 22 spraying the aerosol 14 is sprayed with aerosol in a predetermined direction, the holder for fixing the tubular support 110 according to the area (or size of the tubular support) to form the hydrogen transfer film 130 ( 24 is rotatable to scan and to form a uniform thickness over the entire area during deposition. For uniform film formation on the tubular support 110, the tubular support 110 is mounted on a rotatable holder and rotated at a speed of 1 to 10 rpm. The holder 24 is connected to a rotation driving means (not shown) such as a motor, and is rotatable by driving by the rotation driving means, and the tubular support 110 also rotates in association with the rotation of the holder 24. do.

The film formation on the tubular support 110 will be described in more detail.

As the aerosol is injected from the nozzle 22, the holder 24 or the nozzle 22 is linearly moved in the longitudinal direction of the tubular support 110 (in the direction of the straight arrow in FIGS. 3 and 4), thereby lengthening the tubular support 110. In order to form the film sequentially along the direction, and when the film thickness of the target thickness is formed along the longitudinal direction of the tubular support 110, the tubular support 110 is rotated about its longitudinal direction (round curves in FIGS. 3 and 4). Arrow direction), and the aerosol is sprayed again from the nozzle 22 so that the holder 24 or the nozzle 22 is linearly moved in the longitudinal direction of the tubular support 110 so that the tubular support 110 adjacent to the formed portion is formed. The film formation is sequentially performed on the region of. By repeating the above process, the raw material powder 12 may be deposited on the tubular support 110. At this time, the holder 24 or the nozzle 22 is connected to a driving means (not shown) such as a motor and can be linearly moved vertically or horizontally by a driving force by the driving means. The scan speed at which the holder 24 or the nozzle 22 linearly moves in the longitudinal direction of the tubular support 110 is preferably about 0.5 to 50 cm / min in order to induce deposition of uniform thickness.

Looking at another method of forming a film on the tubular support 110, the aerosol is sprayed from the nozzle 22, the tubular support 110 is rotated in the longitudinal direction axially to form a film sequentially along the circumferential surface of the tubular support 110 When the film of the target thickness is formed along the circumferential surface of the tubular support 110, the holder 24 or the nozzle 22 is linearly moved in the longitudinal direction of the tubular support 110, and at the nozzle 22. As the aerosol is injected again, the tubular support 110 is rotated axially in the longitudinal direction to form a film along the circumferential surface of the tubular support 110 with respect to the region of the tubular support 110 adjacent to the formed portion. By repeating the above process, the raw material powder 12 may be deposited on the tubular support 110.

Referring to another method of forming a film on the tubular support 110, the aerosol is injected from the nozzle 22, the tubular support 110 is rotated about the longitudinal axis and the holder 24 or the nozzle 22 is a tubular support ( The film is formed simultaneously along the circumferential surface and the longitudinal direction of the tubular support 110 by linear movement in the longitudinal direction of the 110, and moves when the linear movement of the holder 24 or the nozzle 22 reaches the limit. The tubular support 110 is rotated about its length in the axial direction while being moved in the opposite direction to the film formation. By repeating the above process, the raw material powder 12 may be deposited on the tubular support 110. The film formation is performed on the tubular support 110 while the rotation and the linear movement of the tubular support 110 are simultaneously performed.

The deposition rate is preferably about 0.1 to 10 μm / min in order to induce the deposition of uniform thickness and to form the hydrogen transfer film 130 of the desired thickness, and the deposition may be performed at room temperature (eg, 10 to 30 ° C.). Can be.

Hydrogen transfer film 130 prepared according to a preferred embodiment of the present invention may be subjected to a heat treatment to strengthen the bond between the particles. When the hydrogen transfer film formed by the aerosol deposition method is heat-treated, it is possible to have more excellent mechanical strength by interparticle bonding. It is preferable to perform the said heat processing at the temperature of about 1000 to 1500 degreeC for about 1 minute-about 10 hours. In the heat treatment step, the temperature is raised to a predetermined temperature increase rate (eg, 10 ° C./min) up to the heat treatment temperature (1000 ° C. to 1500 ° C.), and the heat treatment is performed by maintaining the predetermined time (eg, about 1 minute to about 10 hours) at the heat treatment temperature, It can be carried out by cooling to room temperature.

After the tubular support 110 is fired, the hydrogen transfer film 130 may be formed, but the hydrogen transfer film 130 is coated by the aerosol film formation method without the firing process after the molding process of the tubular support 110. Then, in the heat treatment process of the hydrogen transfer film 130, the baking process of the tubular support 110 may be performed together.

On the outside of the hydrogen transfer film 130, a metal film 140 having hydrogen separation and transfer characteristics is formed to separate hydrogen from a mixed gas containing hydrogen and discharge the hydrogen to the hydrogen transfer film 130. The metal film 140 is made of a film having a porosity smaller than that of the hydrogen transfer film 130 and a denser film than the hydrogen transfer film 130. The metal film 140 having hydrogen separation and transfer properties preferably has a porosity of 0.001 or less and a dense film, and a thickness of 50 μm or less, preferably 1 to 10 μm. The thicker the thickness, the faster the hydrogen transmittance is reduced, resulting in a decrease in the performance of the metal film 140. When the thickness is excessively thin, the metal film 140 may not completely cover the pores of the hydrogen transfer film 130 below the metal film 140, and thus, the mixed gas may leak. The metal layer 140 is made of a palladium (Pd) -based alloy material in which a palladium (Pd) metal or a palladium metal (Pd) and at least one metal selected from cobalt (Co), nickel (Ni), and copper (Cu) are alloyed. It is preferable. The at least one metal selected from cobalt (Co), nickel (Ni) and copper (Cu) is preferably contained in the palladium (Pd) -based alloy 1 to 80 parts by weight based on 100 parts by weight of the palladium (Pd) metal. .

When a mixed gas containing hydrogen, such as a hydrocarbon (C _x H _y ) -based gas, flows into the hydrogen separation membrane module, hydrogen (H ₂ ) passes through the metal membrane 140, the hydrogen transfer membrane 130, and the tubular support 110. ) Are separated. Hydrocarbon (C _x H _y ) -based gas flowing into the hydrogen separation membrane module is a high temperature (for example 300 ~ 900 ℃) and a high pressure (for example 800 ~ 10,000 torr) higher than atmospheric pressure. For example, when methane (CH ₄ ) is used as a hydrocarbon (C _x H _y ) -based gas, the following decomposition reaction occurs by the hydrogen separation membrane module.

[Reaction Scheme 1]

^{_{CH 4 → C + 4H + +}} 4e -

Methane (CH ₄ ) is introduced into the metal film 140 and decomposed into carbon (C), hydrogen ions (H ⁺ ), and electrons, and the hydrogen ions and electrons are tubular through the metal film 140. The hydrogen ions (H ⁺ ) and electrons (e ⁻ ) that are delivered to the support 110 and passed through the metal film 140 undergo recombination, are converted into hydrogen (H ₂ ), and are discharged from the tubular support 110. do. Hydrogen (H ₂ ) is discharged through the tubular support (110) because there are a myriad of pores in the tubular support (110). Carbon (C) decomposed from methane (CH ₄ ) remains on the surface of the metal film 140.

The metal film 140 may use a method such as a deposition method, a spraying method, a wet coating method, or the like. Among the vapor deposition methods, arc deposition, sputtering, evaporation, and implantation methods may be used. In addition, thermal chemical vapor deposition (Thermal Chemical Vapor Deposition), PACVD (Plasma assisted Chemical Vapor Deposition), etc. may be used as chemical vapor deposition. As the thermal spraying method, a thermal spraying method or a plasma spraying method may be used. For example, a plasma spray coating method, a high velocity oxide-fuel (HOVF) coating method, a high temperature thermal spraying method, a cold spray coating process, or a low temperature spray coating method may be applied. Do. Dipping, slip casting, or the like may be used as the wet coating method.

The metal film 140 is preferably palladium (Pd) metal or palladium (Pd) and palladium (Pd) alloyed with one or more metals selected from cobalt (Co), nickel (Ni) and copper (Cu) by sputtering. It may be made of Pd) -based alloy, thereby forming a uniform and dense film. For example, a method of manufacturing the metal film 140 may be obtained by using a (asymmetric) magnetron sputtering method to obtain a film having high adhesion to the hydrogen transfer film 130 and having a temperature of 600 ° C. or less. Since it is possible to maintain a low coating process temperature, it is possible to have a highly bonded coating that does not deform the physical properties of the substrate (a tubular support having a hydrogen transfer film). The metal film 140 is formed of a palladium (Pd) metal or a palladium metal (Pd), cobalt (Co), nickel (Ni) and copper in a sealed chamber of a size that can accommodate a desired substrate (a tubular support having a hydrogen transfer film formed thereon). At least one metal selected from (Cu) may be produced using a raw material having a purity of 99.95% or more composed of an alloyed palladium (Pd) -based alloy. In addition, the raw material is preferably contained in a container of a certain form or manufactured in a target form (target) it is preferable to install divided into 1 to 8 on the upper and lower or inner wall surface in the chamber. In order to increase the bonding strength between the metal film 140 and the hydrogen transfer film 130, it is preferable to use an electrode equipped with a permanent magnet, wherein the permanent magnet is asymmetrical to control the mobility and direction of the deposition material. Can be arranged and used. The power supply used for the deposition of the metal film 140 is preferably an AC type having a frequency of 1 MHz to 400 MHz or a pulsed DC power supply of 5 to 400 KHz. A discharge is generated under vacuum pressure of 0.01 to 10 mmTorr using an applied power source to form a plasma. At this time, Ar or O _{2 is added} to maintain the plasma state and to ensure the stability of the metal film 140 composition and crystal structure. It is preferable to use within the range of ~ 1,000 ml. The deposition rate of a palladium (Pd) metal or a palladium (Pd) -based alloy in which palladium metal (Pd) and at least one metal selected from cobalt (Co), nickel (Ni), and copper (Cu) is alloyed is 0.1 to 1 nm / It is preferable to proceed with the process in the range of sec. Too fast a deposition rate may lower the adhesion between the deposited metal film 140 and the hydrogen transfer film 130, so the deposition rate control as described above is necessary. In order to uniformly deposit the object, the substrate (tubular support having a hydrogen transfer film) is preferably mounted on a rotating shaft connected to the inside or outside of the chamber and rotates at a speed of 1 to 500 rpm. As another method for ensuring high bonding between the hydrogen transfer film 130 and the metal film 140, it is preferable to apply a bias power supply in the range of 1 to 1,000 V to the substrate (the tubular support on which the hydrogen transfer film is formed). Do.

Hereinafter, a method of forming the metal film 140 will be described in more detail with reference to FIGS. 5 to 8.

5 is a conceptual view schematically showing a sputter deposition apparatus for forming a metal film, FIG. 6 is a view schematically showing a flux of particles emitted from a target of the deposition apparatus, and FIGS. 7 and 8 are depositions according to an example. Figures showing the appearance of the device.

5 to 8, a deposition apparatus for forming a metal film 140 includes a target made of a material to be deposited on a substrate (hydrogen transfer film coated (or deposited) on a tubular support) disposed in a deposition chamber ( It is a device to form a plasma around the target, and the material released from the target by the ion bombardment is deposited on the substrate (hydrogen transfer film coated (or deposited) on the tubular support). When a negative voltage is supplied to the target to accelerate ions from the plasma to the target surface and the accelerated ions collide with the target surface, the material to be deposited from the target is released in the opposite direction to the direction of ion incidence, The material to be transferred to the substrate (hydrogen transfer film coated (or deposited) on the tubular support) is coated on the surface of the hydrogen transfer film 130.

In the deposition apparatus for forming the metal film 140, the substrate illustrated in FIG. 5 is disposed in the deposition chamber 200. The inner wall of the deposition chamber 200 is coated with an insulator and sealed electrically. The windows 280a and 280b provided to observe the inside may be provided, and an outlet 275 for discharging the gas may be provided.

The substrate is provided to be able to rotate and may also be provided to be able to rotate. The substrate is mounted in a rotatable holder 12 for uniform deposition and rotated at a constant speed (eg, 1-100 sec / cycle). The holder 212 is connected to the first rotation driving means 216 such as a motor, and is rotatable by driving by the first rotation driving means 216, and the substrate is interlocked with the rotation of the holder 212 to rotate. Will be. In addition, the holder 212 is connected to the rotatable holder support 214, the holder support 214 is connected to the second rotary drive means 218, such as a motor, to the second rotary drive means 218 The holder support 214 is rotatable by driving, and the holder 212 revolves at a constant speed (for example, 1 to 100 sec / cycle) according to the rotation of the holder support 214, and thus the substrate is also rotated. It interlocks and becomes idle.

Holder 212 is provided by being heated by a heating means (not shown) to be controlled to a predetermined temperature (for example, 300 ~ 600 ℃). By heating the temperature of the holder 212 to a predetermined temperature (for example, 300 ~ 600 ℃) by using a heating means to be deposited in a state where the substrate is heated to a certain temperature, the physical properties of the deposited metal film is improved It is economical and can be simplified since subsequent heat treatment at high temperature is not necessary.

The vacuum pump 270 is connected to the deposition chamber 200 to maintain the inside of the deposition chamber 200 at a low pressure to make a vacuum state and serves to discharge the gas present in the deposition chamber 200 to the outside. As a result, the pressure in the deposition chamber 200 may be maintained at about 10 ⁻⁷ to 10 ⁻¹ Torr.

Two targets 220 and 230 are disposed at a predetermined angle θ relative to the substrate, and the angle θ formed by the two targets 220 and 230 is a flux of a material to be deposited onto the substrate. In order to reach 232 evenly, it is in the range 90 ° <θ <180 °. The substrate is positioned in an area A where an area in which the flux 232 of particles sputtered from the first target 220 is distributed and an area in which the flux 232 of the particles sputtered from the second target 230 are distributed are overlapped. The substrate is then rotated and revolved in the region A. As shown in FIG.

Palladium (Pd) metal may be mounted on the first target 20, and metal such as cobalt (Co), nickel (Ni), copper (Cu), or an alloy thereof may be mounted on the second target 230. have. Metals such as cobalt (Co), nickel (Ni), copper (Cu) or alloys thereof serve to prevent pores or cracks in subsequent heat treatment processes to form dense palladium (Pd) based alloys.

The first target 220 is connected to the first power supply 240 to supply a DC voltage, and the second target 230 is supplied with a pulse voltage that is a voltage at which polarities are alternately connected by connecting the second power supply 250. do. The first power supply unit 240 and the second power supply unit 250 are provided to be controlled independently of each other. The DC voltage supplied from the first power supply 240 may be independently supplied to the first target 220, and the pulse voltage supplied from the second power supply 240 may be independently supplied to the second target 230. have. Accordingly, the intensity of ion bombardment of the two targets 220 and 230 may be adjusted by independently controlling the power supplied to the first target 220 and the second target 230, and thus the deposition on the substrate surface. It is possible to control the film quality.

The first target 220 is shielded by the first shutter 225a, and the first shutter 225a is connected to the driving means 292a such as a motor through the connecting portion 290a and connected to the first target 295. In the case of depositing the mounted material, it is opened by the driving means 292a for driving opening and closing of the first shutter 225a. The second target 230 is shielded by the second shutter 225b, and the second shutter 225b is connected to the driving means 292b such as a motor through the connecting portion 290b and to the second target 230. In the case of depositing the mounted material, it is opened by driving means 292b for driving opening and closing of the second shutter 225b. The first shutter 225a and the second shutter 225b are opened and closed by driving means, respectively, and the first shutter 225a and the second shutter 225b are provided to be opened and closed independently of each other.

In addition, a third target 295 may be further provided, and the third target 295 is used when forming a composite film made of three or more materials on a substrate. The third target 295 is also shielded by a shutter (not shown), and the shutter shielding the third target 295 is connected to a driving means (not shown) such as a motor through the connecting portion 290c and the third target. In the case of depositing a material mounted at 295, the material is opened by the driving means for driving opening and closing of the shutter. A power supply unit (not shown) is also connected to the third target 295 to supply a required voltage.

Permanent magnets or electromagnets (not shown) are disposed on the rear of the targets 220 and 230 so that a magnetic field may be formed around the targets 220 and 230. The permanent magnets or electromagnets may be formed of a single magnet, It may also be arranged. The permanent magnet or electromagnet forms a magnetic field near the target surface having a component parallel to the surfaces of the targets 220 and 230. The magnetic field having a component parallel to the surface of the target 220 and 230 serves to trap electrons in the plasma near the surface of the target 220 and 230, thereby generating a lot of collisions near the surface of the target 220 and 230. .

The gas supply means 260 may include a mass flow controller (MFC) connected to argon (Ar) gas, nitrogen (N ₂ ) gas, or a mixed gas of argon (Ar) and nitrogen (N ₂ ) to the connection pipe 265. ) Is supplied into the deposition chamber 200 through (not shown). When the argon (Ar) gas, the nitrogen (N ₂ ) gas or the mixed gas of argon (Ar) and nitrogen (N ₂ ) is introduced into the deposition chamber 200 by the gas supply means 260, the first target 220. ) And the power applied to the second target 230 make argon (Ar) gas, nitrogen (N ₂ ) gas or a mixed gas of argon (Ar) and nitrogen (N ₂ ) into a plasma state, and positively charged ions in the plasma state. Palladium (Pd) metal particles mounted on the first target 220 and cobalt (Co) mounted on the second target 230 by colliding with the first target 220 and the second target 230 with considerable energy, Metal particles such as nickel (Ni), copper (Cu), or alloys thereof are sputtered from the first target 220 and the second target 230.

Sputtered materials 225 and 235 are incident on the substrate and are to be deposited. Since the substrate rotates and revolves, particles sputtered from the first target 220 and the second target 230 may be evenly deposited without being biased. In the deposition process, DC power is applied to the first target 220 so that the palladium (Pd) metal particles are sputtered from the first target 220, and then a pulse voltage is applied to the second target 230 to cobalt (Co) and nickel. Metal particles such as (Ni), copper (Cu) or alloys thereof are sputtered from the second target 230 so that the palladium (Pd) metal particles are first deposited on the substrate and cobalt (Co), nickel (Ni), copper Metal particles such as (Cu) or alloys thereof may be deposited in such a manner as to be deposited later, and conversely, a pulse voltage is applied to the second target 230 to cobalt (Co) and nickel (Ni). ), Metal particles such as copper (Cu) or alloys thereof are sputtered from the second target 230, and then a DC power is applied to the first target 220 so that the palladium (Pd) metal particles are formed on the first target 220. Sputtered on the substrate such as cobalt (Co), nickel (Ni), copper (Cu) or alloys thereof The deposition may be carried out in such a manner that metal particles are deposited first and palladium (Pd) metal particles are deposited later, and a DC power is applied to the first target 220 and a pulse is applied to the second target 230. Palladium (Pd) metal particles and metal particles such as cobalt (Co), nickel (Ni), copper (Cu), or alloys thereof may be simultaneously deposited on a substrate by applying a voltage. At this time, the metal such as cobalt (Co), nickel (Ni), copper (Cu) or an alloy thereof contains 1 to 80 parts by weight based on 100 parts by weight of the palladium (Pd) metal in the palladium (Pd) -based alloy formed after deposition. It is desirable to adjust. When only the palladium (Pd) metal is coated or deposited on the substrate, the palladium (Pd) metal may be mounted only on the first target 20 to perform coating or deposition. When using a palladium (Pd) -based alloy alloyed with at least one metal selected from palladium metal (Pd), cobalt (Co), nickel (Ni), and copper (Cu), the first target 20 may be used as a deposition material. The coating or deposition may be performed by mounting a palladium (Pd) -based alloy alloyed with a palladium metal (Pd) and at least one metal selected from cobalt (Co), nickel (Ni), and copper (Cu).

The metal film 140 coated or deposited is heat treated at 300 to 1200 ° C. for a predetermined time (for example, 1 minute to 6 hours) to obtain a dense metal film 140 capable of hydrogen separation and transfer. The hydrogen transfer film 130 may not be sintered before the metal film 140 is coated. Although the metal film 140 may be formed after the hydrogen transfer film 130 is fired, the palladium (Pd) metal or the palladium metal (Pd) may be formed without the firing process after the hydrogen transfer film 130 is coated. And a palladium (Pd) -based alloy in which at least one metal selected from cobalt (Co), nickel (Ni), and copper (Cu) is alloyed, and then the hydrogen transfer film 130 in the heat treatment process of the metal film 140. The firing process may be performed together. In either case, however, the metal film 140 needs to be sufficiently densified after the final heat treatment.

The metal layer 140 formed on the hydrogen transfer layer 130 may also be manufactured by the following method, for example, by dissolving an organic precursor including palladium (Pd) in a suitable solvent, the hydrogen transfer layer 130. It can be coated by dipping. The hydrogen transfer layer 130 coated with the organic precursor may be heat-treated to remove the organic material and form a dense metal layer 140. The heat treatment for forming a dense metal film may be performed by heating at a rate of 2 to 50 ° C. per minute in an air atmosphere, maintaining the temperature at 300 to 1200 ° C. for a predetermined time (for example, 1 minute to 6 hours), and then naturally cooling the same.

The following experiment was conducted to form the above-described hydrogen separation membrane module.

<Experimental Example>

Yttria-stabilized zirconia (YSZ) powder, carboxymethyl cellulose (CMC) as a pore forming agent, and ethanol as a solvent were added and kneaded. In consideration of the pore size of the tubular support 110, the yttria stabilized zirconia (YSZ) powder had a particle size of about 1 to 50 μm.

Molding using an extrusion method to form a tube 120 inside the tubular support (110). It was shape | molded so that solid content might be 70 to 85% of range by the extrusion method.

When the tube 120 is formed inside the tubular support 110, the final tubular support 110 was manufactured by baking for 1 hour at a temperature of 1310 ℃. In the firing process, the pore-forming agent is burned away at a predetermined temperature (eg, 300 ° C. to 600 ° C.) or more, and pores are formed at the burned-out place, and the tubular support 110 is porous.

Alumina (Al ₂ O ₃ ) powder, which is a raw material powder, was prepared and mounted on the aerosol supply unit 10 of the aerosol film-forming apparatus. The alumina (Al ₂ O ₃ ) powder was used having a particle size of 0.3 ~ 6㎛.

The alumina (Al ₂ O ₃ ) powder was vibrated using the vibrator 18 so that flocculation between the raw material powder particles could be easily suspended. At this time, the rotation speed of the vibrator 18 was set to about 200 rpm.

The carrier gas was supplied from the carrier gas supply unit 30 to the aerosol supply unit 10, and the flow rate of the carrier gas was supplied to the aerosol supply unit 10 through the conduit 34 while controlling the flow rate of the carrier gas through the flow control means (MFC) 32. The alumina (Al ₂ O ₃ ) powder was suspended. Helium (He) gas was used as the carrier gas, and the flow rate of the carrier gas was set in the range of 4 to 30 SLPM.

The raw material powder suspended by the vibrator 18 and the carrier gas forms the aerosol 14, and the formed aerosol 14 is formed from the aerosol supply unit 10 through the conduit 16 by the pressure difference. It was supplied to the nozzle 22 inside. The nozzle 22 is equipped with the injection hole of 10 mm x 0.4 mm.

Before the aerosol 14 is supplied to the nozzle 22, the inside of the film forming chamber 20 is decompressed by a pressure controller 40 at a vacuum of about 0.4 torr, and the pressure inside the film forming chamber 20 at the time of film forming is 10. It was maintained at a vacuum degree of ˜760 torr.

When the pressure of the deposition chamber 20 is formed, the desired deposition conditions are formed, the aerosol 14 is supplied from the aerosol supply unit 10 to the nozzle 22 of the deposition chamber 20 to supply yttria-stabilized zirconia; YSZ) was formed to be sprayed toward the tubular support (110). The distance between the injection port of the nozzle 22 and the tubular support 110 was about 1.5 cm. The aerosol sprayed on the tubular support 110 is formed while being pulverized by the impact to form a film.

In the method of forming a film on the tubular support 110, the tubular support 110 is installed in a holder 24 that is movable up and down, left and right, and is rotatable, and the aerosol 14 is sprayed through the nozzle 22 to hold the holder 24. ) Is formed in the tubular support 110 in a predetermined area while moving in the longitudinal direction of the tubular support 110, and when the film is formed in a predetermined area along the longitudinal direction of the tubular support 110, the holder is rotatable. The holder 240 moves in the longitudinal direction of the tubular support 110 while causing the tubular support 110 to be rotated about its longitudinal direction through the 24 and causing the aerosol 14 to be ejected again from the nozzle 22. The deposition was performed on the region of the tubular support 110 adjacent to the deposited portion.

At this time, in order to form a film with a uniform thickness over the entire area of the tubular support 110 during film formation, the scan speed of the holder 24 was set to about 10 mm / min, and the film formation proceeded at room temperature.

In the deposition chamber 200 of the deposition apparatus for forming the metal film 140, a substrate formed by coating the hydrogen transfer film 130 on a tubular tubular support 110 made of yttria stabilized zirconia (YSZ) is disposed, The substrate is rotated at 25 sec / cycle and idle at 35 sec / cycle.

The vacuum chamber 270 connected to the deposition chamber 200 was used to maintain the inside of the deposition chamber 200 at a low pressure of about 10 ⁻¹ Torr to bring it into a vacuum state.

The angle θ formed between the first target 220 and the second target 230 is about 150 ° to evenly reach the flux 232 of the material to be deposited onto the substrate. The region in which the flux 232 of the particles sputtered from the first target 220 is distributed and the region in which the flux 232 of the particles sputtered from the second target 230 are distributed are located in the overlapping area A. The substrate was allowed to rotate and revolve in area A.

Palladium (Pd) is mounted on the first target 220, copper (Cu) is mounted on the second target 230, and 0.4V DC is applied to the first target 220 through the first power supply 240. The voltage was supplied, and the pulse voltage was supplied by applying 600 W of power to the second target 230 through the second power supply 250. Independently controlling the power supplied to the first target 220 and the second target 230 to control the intensity of the ion bombardment (ion bombardment) for the two targets 220, 230 to the surface of the hydrogen transfer film 130 The film quality to be deposited was controlled. Permanent magnets are disposed on the rear surfaces of the targets 220 and 230 so that magnetic fields may be formed around the targets 220 and 230.

Argon (Ar) gas is supplied into the deposition chamber 200 through the gas supply means 260, so that the argon (Ar) gas is plasma by the power applied to the first target 220 and the second target 230. And the palladium (Pd) metal particles and the second target 230, which are made of and are mounted on the first target 220 due to the collision of the positively charged ions in the plasma state with a considerable energy of the first target 220 and the second target 230. Copper (Cu) metal particles attached to the sputtered from the first target 220 and the second target 230.

The sputtered materials 225 and 235 were incident on the hydrogen transfer film 130 to be deposited. As described above, by applying a DC power supply to the first target 220 and applying a pulse voltage to the second target 230, the palladium (Pd) metal particles and the copper (Cu) metal particles are formed on the hydrogen transfer layer 130. At the same time, the deposition was performed, and the substrate was allowed to rotate and revolve so that the particles sputtered from the first target 220 and the second target 230 were deposited. The temperature of the holder 212 was heated to 400 ° C. (673K) using a heating means, and the deposition was performed while maintaining the temperature of the substrate at about 400 ° C.

Heat treatment was performed to enhance the interparticle bonding. The heat treatment was carried out for 2 hours at a temperature of 1000 ℃, it was carried out by cooling to room temperature.

9 is a photograph showing a hydrogen separation membrane module prepared according to the experimental example. 10 is a scanning electron microscope (SEM) photograph showing a cross section of a hydrogen separation membrane module manufactured according to the experimental example.

9 and 10, it can be seen that the metal film made of Pd-Cu is formed densely, and the hydrogen transfer film made of Al ₂ O ₃ is more effective than the tubular support made of yttria stabilized zirconia (YSZ). It can be seen that it is formed densely.

FIG. 11 is a scanning electron microscope (SEM) photograph of the surface of the metal film prepared according to the Experimental Example after sputter deposition and heat treatment, and FIG. 12 is a surface of the metal film prepared according to the Experimental Example after sputter deposition and heat treatment. Scanning electron microscope (SEM) image taken.

Referring to FIGS. 11 and 12, it can be seen that pores or cracks are formed on the surface before the heat treatment, but a dense film without pores or cracks is formed on the surface after the heat treatment. It is believed that a dense Pd-Cu film was formed while copper (Cu), which is a binary metal, prevented pores or cracks by heat treatment.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, This is possible.

10: aerosol supply unit 12: raw material powder
14: Aerosol 16: Conduit
18: oscillator 20: deposition chamber
22: nozzle 24: holder
30: carrier gas supply unit 32: flow control means
34: conduit 40: pressure control unit
42: rotary pump 44: booster pump
110: tubular support 120: tube
130: hydrogen transfer film 140: metal film
212: holder 214: holder support
216: first rotation drive means 218: second rotation drive means
220: first target 225a, 225b: shutter
230: second target 232: flux
240: first power supply unit 250: second power supply unit
260: gas supply means 265: connector
270: vacuum pumps 292a, 292b: drive means
295: third target

Claims (15)

A tubular support formed of a ceramic material having a pore formed therein and providing a passage through which hydrogen gas is discharged;
A hydrogen transfer film made of ceramic material having nano-sized pores formed thereon to transfer hydrogen to the tubular support; And
It is formed on the outside of the hydrogen transfer film and has a hydrogen separation and transfer properties to separate the hydrogen from the mixed gas containing hydrogen to discharge to the hydrogen transfer film,
The hydrogen transfer membrane has an average pore size of 0.01-1 μm and a porosity of 0.1-0.2, which is smaller than the porosity of the tubular support and is a denser membrane than the tubular support.
The metal membrane is a tubular hydrogen separation membrane module, characterized in that the porosity is less than the porosity of the hydrogen transfer membrane and made of a denser than the hydrogen transfer membrane.
The tubular hydrogen separation membrane module of claim 1, wherein the metal membrane is made of palladium (Pd) metal having a higher melting point than 300 ° C. to 900 ° C. at which the hydrogen separation membrane module is used.
According to claim 1, wherein the metal film is Palladium (Pd) metal having a higher melting point than 300 ~ 900 ℃, the temperature at which the hydrogen separation membrane module is used and cobalt (Co), nickel (Ni) and copper having a lower melting point than palladium (Pd) At least one metal selected from (Cu) is composed of an alloyed palladium (Pd) -based alloy,
At least one metal selected from cobalt (Co), nickel (Ni), and copper (Cu) may be contained in the palladium (Pd) -based alloy in an amount of 1 to 80 parts by weight based on 100 parts by weight of the palladium (Pd) metal. Tubular hydrogen separation membrane module.
The method of claim 1, wherein the hydrogen transfer membrane is stabilized silicon carbide (SiC), alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ), yttria stabilization does not occur at a temperature 300 ~ 900 ℃ the hydrogen separation membrane module is used A tubular hydrogen separation membrane module comprising at least one ceramic material selected from zirconia (yttria-stabilized zirconia) and aluminum titanate (AlTiO ₃ ).
According to claim 1, The tubular support is a silicon carbide (SiC), alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ), yttria stabilization does not occur at a temperature 300 ~ 900 ℃ the hydrogen separation membrane module is used It is made of at least one ceramic material selected from zirconia (yttria-stabilized zirconia) and aluminum titanate (AlTiO ₃ ), characterized in that the tubular support has an average pore size of 0.1 ~ 100㎛ and porosity is 0.2 ~ 0.4 Tubular hydrogen separation membrane module.
Mixing and kneading a raw material, a pore-forming agent, and a solvent of a ceramic material which do not cause deformation at a temperature at which the hydrogen separation membrane module is used;
Molding and baking the kneaded product so that a tube providing a passage through which hydrogen gas is discharged is formed, and then baking to form a tubular support made of a porous ceramic material;
Sealing the tube inside the tubular support so as not to be exposed, and forming a hydrogen transfer film of ceramic material on the tubular support having nano-sized pores formed thereon to transfer hydrogen to the tubular support;
Sealing a tube inside the tubular support so as not to be exposed, and having a hydrogen separation and transfer characteristic to form a metal film on the outside of the hydrogen transfer film to separate hydrogen from the mixed gas containing hydrogen and discharge the hydrogen to the hydrogen transfer film; And
Heat-treating the resultant formed metal film,
The hydrogen transfer membrane has an average pore size of 0.01-1 μm and a porosity of 0.1-0.2, which is smaller than the porosity of the tubular support and is formed into a denser membrane than the tubular support.
The metal membrane is a tubular hydrogen separation membrane module manufacturing method, characterized in that the porosity is less than the porosity of the hydrogen transfer membrane is formed of a denser than the hydrogen transfer membrane.
The method of claim 6, wherein the metal film is formed of palladium (Pd) metal having a higher melting point than 300 to 900 ° C, which is a temperature at which the hydrogen separation membrane module is used.
According to claim 6, wherein the metal film is Palladium (Pd) metal having a higher melting point than 300 ~ 900 ℃, the temperature at which the hydrogen separation membrane module is used Cobalt (Co), nickel (Ni) and copper having a lower melting point than palladium (Pd) At least one metal selected from (Cu) is formed of an alloyed palladium (Pd) -based alloy,
At least one metal selected from cobalt (Co), nickel (Ni), and copper (Cu) is contained in the palladium (Pd) -based alloy in an amount of 1 to 80 parts by weight based on 100 parts by weight of the palladium (Pd) metal. Method for producing a tubular hydrogen separation membrane module.
The method of claim 6, wherein the forming of the metal film on the outside of the hydrogen transfer film,
A deposition chamber, a tubular support having the hydrogen transfer film disposed in the deposition chamber, a first target for supplying a palladium (Pd) metal disposed in the deposition chamber and to be deposited onto the surface of the hydrogen transfer film, and the deposition A second target for supplying cobalt (Co), nickel (Ni), copper (Cu), or an alloy thereof, disposed in the chamber and to be deposited onto the surface of the hydrogen transfer film; and for supplying voltage to the first target. Preparing a deposition apparatus including a first power supply, a second power supply for supplying a voltage to the second target, and gas supply means for supplying a gas for plasma formation in the deposition chamber;
A method of manufacturing a tubular hydrogen separation membrane module, characterized in that the metal membrane is formed by rotating the tubular support on which the hydrogen transfer membrane is formed in conjunction with the rotation of the holder on which the hydrogen carrier membrane is formed.
10. The method of claim 9, wherein the metal membrane is formed by revolving the tubular support on which the hydrogen transfer film is formed at regular intervals in association with rotation of the holder support for supporting the holder.
The method of claim 9, wherein the first target and the second target are in a range of 90 ° <θ <180 ° based on the tubular support on which the hydrogen transfer film is formed so that the flux of the material to be deposited reaches the hydrogen transfer film evenly. The tubular support on which the hydrogen transfer film is formed is disposed at an angle θ of, and the region where the flux of the particles sputtered from the first target is distributed and the region where the flux of the particles sputtered from the second target are distributed are overlapped. A method of manufacturing a tubular hydrogen separation membrane module, characterized in that to form the metal film to be placed in.
10. The method of claim 9, wherein the heating means for controlling the temperature of the tubular support on which the hydrogen transfer film is formed to maintain the temperature of the tubular support on which the hydrogen transfer film is formed in a range of 300 ~ 600 ℃ constant to form the metal film. Method for producing a tubular hydrogen separation membrane module.
The method of claim 6, wherein the hydrogen transfer membrane is stabilized silicon carbide (SiC), alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ), yttria stabilization does not occur at a temperature 300 ~ 900 ℃ the hydrogen separation membrane module is used Method for producing a tubular hydrogen separation membrane module, characterized in that formed from at least one ceramic material selected from zirconia (yttria-stabilized zirconia) and aluminum titanate (AlTiO ₃ ).
The method of claim 6, wherein the forming of the hydrogen transfer film on the tubular support,
Installing the tubular support in cooperation with a rotatable holder provided in the deposition chamber;
Maintaining the inside of the deposition chamber at a constant pressure;
Through the flow control means, the carrier gas is fed to the raw powders of silicon carbide (SiC), alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ), yttria-stabilized zirconia and aluminum titanate (AlTiO _3). Aerosolizing the raw material powder by supplying it to a space in which at least one ceramic material powder is selected;
Supplying the formed aerosol to a nozzle in the deposition chamber by a pressure difference; And
While the distance between the nozzle of the nozzle and the tubular support to be deposited is kept constant in the range of 2 to 20 mm, the aerosol is sprayed toward the tubular support so that the aerosol sprayed on the tubular support is formed by being crushed by impact. Method for producing a tubular hydrogen separation membrane module comprising the step of forming a hydrogen transfer membrane.
The method of claim 6, wherein the tubular support is stabilized silicon carbide (SiC), alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ), yttria stabilization does not occur at a temperature 300 ~ 900 ℃ the hydrogen separation membrane module is used It is formed of at least one ceramic material selected from zirconia (yttria-stabilized zirconia) and aluminum titanate (AlTiO ₃ ),
A plurality of pores are formed in the tubular support through the firing, the average pore size of the tubular support is 0.1 ~ 100㎛ and porosity is 0.2 ~ 0.4 method for producing a tubular hydrogen separation membrane module.

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