KR101247129B1 - Method for separating carbon from the hydrocarbon gas - Google Patents

Abstract

The present invention provides a step of preparing a hydrogen separation membrane module by forming a hydrogen separation membrane and a catalyst layer having a hydrogen ion conductivity on the porous support, and hydrocarbon (C _x H _y ), where x is equal to or greater than 1, and y Is a real number equal to or greater than 2) making the gas at a temperature of 300 to 900 ° C. and a pressure higher than atmospheric pressure, and the hydrocarbon (C _x H _y ), where x is a real number equal to or greater than 1, y is a real number equal to or greater than 2) introducing a gas into the hydrogen separation membrane module including a catalyst layer, a hydrogen separation membrane having a hydrogen ion conductivity and a porous support, wherein the hydrocarbon (C _x H _y ) (where x is Real number equal to or greater than 1, real number equal to or greater than 2) promotes decomposition of carbon (C) and hydrogen (H) as the gas passes through the catalyst layer, and the hydrogen passes through the hydrogen separation membrane. Decomposed into ions and electrons, the hydrogen ions And electrons are delivered to the porous support through a hydrogen separation membrane, and the hydrogen ions and electrons are recombined while passing through the porous support to be discharged as hydrogen (H ₂ ) gas, and the hydrogen separation membrane module is cooled. It relates to a method for separating carbon from a hydrocarbon-based gas comprising the step of desorbing carbon (C) located on the surface of the catalyst layer. According to the present invention, high-purity carbon can be separated from a hydrocarbon-based fuel by direct cracking of a hydrocarbon-based fuel using a hydrogen separation membrane module including a catalyst layer, a hydrogen separation membrane having hydrogen ion conductivity, and a porous support. have.

Description

Method for separating carbon from the hydrocarbon gas

The present invention relates to a hydrogen separation method, and more particularly, to a method for separating carbon from a hydrocarbon-based gas using a hydrogen separation membrane module formed on a catalyst layer, a hydrogen separation membrane having a hydrogen ion conductivity and a porous support.

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, there is a difficulty in producing a hydrogen separation membrane having a uniform pore structure and has not reached the stage of obtaining high purity hydrogen.

On the other hand, gas such as methane (CH ₄ ) is mainly generated in industrial sites, landfills, etc., and the generated gas is mostly discarded, causing environmental pollution, and thus recycling measures are required.

The problem to be solved by the present invention is to separate the high-purity carbon from the hydrocarbon-based fuel by direct cracking the hydrocarbon-based fuel using a hydrogen separation membrane module comprising a catalyst layer, a hydrogen separation membrane having a hydrogen ion conductivity and a porous support. To provide a way to do it.

The present invention provides a step of preparing a hydrogen separation membrane module by forming a hydrogen separation membrane and a catalyst layer having a hydrogen ion conductivity on the porous support, and hydrocarbon (C _x H _y ), where x is equal to or greater than 1, and y Is a real number equal to or greater than 2) making the gas at a temperature of 300 to 900 ° C. and a pressure higher than atmospheric pressure, and the hydrocarbon (C _x H _y ), where x is a real number equal to or greater than 1, y is a real number equal to or greater than 2) introducing a gas into the hydrogen separation membrane module including a catalyst layer, a hydrogen separation membrane having a hydrogen ion conductivity and a porous support, wherein the hydrocarbon (C _x H _y ) (where x is Real number equal to or greater than 1, real number equal to or greater than 2) promotes decomposition of carbon (C) and hydrogen (H) as the gas passes through the catalyst layer, and the hydrogen passes through the hydrogen separation membrane. Decomposed into ions and electrons, the hydrogen ions And electrons are delivered to the porous support through a hydrogen separation membrane, and the hydrogen ions and electrons are recombined while passing through the porous support to be discharged as hydrogen (H ₂ ) gas, and the hydrogen separation membrane module is cooled. It provides a method for separating carbon from a hydrocarbon-based gas comprising the step of desorbing carbon (C) located on the surface of the catalyst layer.

The hydrocarbon (C _x H _y ) (where x is a real number greater than or equal to 1 and y is a real number greater than or equal to 2) is based on methane (CH ₄ ), ethane (C ₂ H ₆ ), propane ( C ₃ H ₈ ) and butane (C ₄ H ₁₀ ) may be one or more gases.

The pressure higher than the atmospheric pressure is preferably a pressure in the range of 800 to 10,000 torr.

The catalyst layer is preferably formed of at least one metal selected from Pt, Ni, Pd, Ag, Mo, and Co.

The hydrogen separation membrane is BaCe _x YM _{1- x} O ₃ , where M is La, Y, Yb, Ga, Gd, In or Ge, x is real and 0 ≦ x <1, SrCe _x YM _{1- x} O ₃ , where M is La, Y, Yb, Ga, Gd, In, or Ge, x is a real number and 0 ≦ x <1, LaSr _x M _{1- x} O ₃ , where M is La, Y , Yb, Ga, Gd, In, or Ge, x is a real number and 0 ≦ x <1, BaCe _x M _{1- x} O ₃ , where x is a real number and 0 <x <1, and M is Y , At least one rare earth element selected from La, Er, Eu, and Gd, BaZr _x M _{1 -x} O ₃ , where x is a real number, 0 <x <1, and M is Y, La, Er, Eu, and At least one rare earth element selected from Gd, BaCe _x Zr _y M _{1 -xy} O ₃ (where x and y are real numbers, 0 <x <1, 0 <y <1, 0 <x + y <1) , M is at least one rare earth element selected from Y, La, Er, Eu, and Gd), SrCe _x M _{1 -x} O ₃ (where x is a real number, 0 <x <1, and M is Y, La, At least one rare earth element selected from Er, Eu and Gd) and SrZr _x M _{1 -x} O ₃ (F Where x is a real number, 0 <x <1, and M is one or more perovskite materials selected from the group consisting of one or more rare earth elements selected from Y, La, Er, Eu, and Gd) Can be.

In the hydrogen separation membrane, it is preferable to use a perovskite material in which the porosity of the hydrogen separation membrane is equal to or smaller than 0.05 and the hydrogen ion conductivity (log σT) is equal to or larger than 0.01 measured at 900 ° C.

The porous support is preferably formed of at least one material selected from SiC, Al ₂ O ₃ , ZrO _2, and AlTiO ₃ , which are ceramic materials that do not cause deformation at 300 to 900 ° C. at which the hydrogen separation membrane module is used.

It is preferable to use the porous support having an average pore size of 0.1 to 100 µm and a porosity of 0.1 to 0.7.

The preparing of the hydrogen separation membrane module may further include forming a second catalyst layer between the hydrogen separation membrane and the porous support to promote a recombination reaction of hydrogen ions and electrons and to improve electron conductivity. The second catalyst layer is preferably formed of at least one metal selected from Pt, Ni, Pd, Ag, Mo, and Co.

The porous support may be formed in a tubular shape in which a tube providing a passage through which hydrogen gas is discharged is formed, the hydrogen separation membrane may be formed outside the porous support, and the catalyst layer may be formed outside the hydrogen separation membrane. have.

The method may further include forming a second catalyst layer between the porous support and the hydrogen separation membrane to promote a recombination reaction of hydrogen ions and electrons and to improve electron conductivity. The second catalyst layer may include Pt, Ni, Pd, It is preferable to form with at least 1 sort (s) of metal chosen from Ag, Mo, and Co.

The porous support is formed in a tubular shape in which a tube providing a passage through which the hydrocarbon-based gas is introduced, the hydrogen separation membrane is formed inside the porous support, and the catalyst layer is formed inside the hydrogen separation membrane. Can be formed.

The method may further include forming a second catalyst layer between the porous support and the hydrogen separation membrane to promote a recombination reaction of hydrogen ions and electrons and to improve electron conductivity. The second catalyst layer may include Pt, Ni, Pd, It is preferable to form with at least 1 sort (s) of metal chosen from Ag, Mo, and Co.

When the hydrogen separation membrane is formed, conductive metal nanoparticles or conductive ceramic nanoparticles having a size of 10 to 200 nm for imparting electronic conductivity to hydrogen ion conductivity are added to the hydrogen separation membrane, and hydrogen is formed as the conductive metal nanoparticles. At least one metal selected from Pt, Ni, Pd, Ag, Mo, Fe, and Co, having a melting point higher than the temperature at which the membrane module is used, is 300 to 900 ° C. The ceramic nanoparticles are CeO ₂ , SnO ₂ , WO _3. It is preferable to use at least one material selected from SiC.

When forming the hydrogen separation membrane, the deposition chamber, the porous support disposed in the deposition chamber, a first target for supplying a first material disposed in the deposition chamber to be deposited on the surface of the porous support, A second target disposed in a deposition chamber and configured to supply a second material to be deposited onto the surface of the porous support; a first power supply configured to supply voltage to the first target; and supplying voltage to the second target. Preparing a deposition apparatus including a second power supply for supplying, and a gas supply means for supplying a gas for plasma formation in the deposition chamber, the porous support is rotated in conjunction with the rotation of the holder is mounted By depositing the hydrogen separation membrane on the porous support.

The hydrogen support may be formed by depositing the hydrogen separation membrane on the porous support by interlocking with the rotation of the holder support for supporting the holder.

The first target and the second target are disposed at an angle θ in the range of 90 ° <θ <180 ° with respect to the porous support so that the flux of the material to be deposited reaches the porous support evenly, and the porosity The support is formed by depositing the hydrogen separation membrane on the porous support so as to be positioned in a 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 is distributed. It is desirable to.

The heating means for controlling the temperature of the porous support is preferably formed by depositing the hydrogen separation membrane on the porous support by maintaining a constant temperature of the porous support in the range 300 ~ 600 ℃.

The preparing of the hydrogen separation membrane module may include: (a) installing a porous support interlocked with a rotatable holder provided in the deposition chamber, (b) maintaining the inside of the deposition chamber at a constant pressure, and (c ) The carrier gas is passed through the flow control means, BaCe _x YM _{1 -x} O ₃ , where M is La, Y, Yb, Ga, Gd, In or Ge, and x is real and 0≤x <1. ), SrCe _x YM _{1 -x} O ₃ , where M is La, Y, Yb, Ga, Gd, In or Ge, x is a real number and 0≤x <1, LaSr _x M _{1 -x} O ₃ (Where M is La, Y, Yb, Ga, Gd, In, or Ge, x is a real number and 0 ≦ x <1), BaCe _x M _{1- x} O ₃ (where x is a real number and 0 < x <1, M is one or more rare earth elements selected from Y, La, Er, Eu, and Gd, BaZr _x M _{1- x} O ₃ (where x is a real number, 0 <x <1, and M is One or more rare earth elements selected from Y, La, Er, Eu, and Gd), BaCe _x Zr _y M _{1 -xy} O ₃ , where x and y are real and 0 < x <1, 0 <y <1, 0 <x + y <1, M is at least one rare earth element selected from Y, La, Er, Eu and Gd, SrCe _x M _{1 -x} O ₃ (where x is a real number, 0 <x <1, M is at least one rare earth element selected from Y, La, Er, Eu and Gd) and SrZr _x M _{1- x} O ₃ (where x is a real number and 0 < x <1, M is at least one perovskite oxide powder selected from at least one rare earth element selected from Y, La, Er, Eu, and Gd), and at least one oxide selected from ZnO, NiO, CuO, and CoO Aerosolizing the raw material powder by supplying it to a space where powder is placed; (d) supplying the formed aerosol to a nozzle in the deposition chamber by a pressure difference, and (e) between the nozzle of the nozzle and the porous support to be deposited The aerosol is sprayed toward the porous support while maintaining a constant distance in the range of 2 to 20 mm Forming a hydrogen separation membrane having a mixed conductivity by forming an aerosol sprayed onto the porous support by pulverization by impact, and (f) heat-treating to improve mechanical strength by strengthening interparticle bonding of the hydrogen separation membrane. And, in the step (e), the aerosol is injected from the nozzle to the linear movement of the holder or the nozzle in the longitudinal direction of the porous support to form a film sequentially along the longitudinal direction of the porous support, When the film having a target thickness is formed along the longitudinal direction of the porous support, the porous support is rotated about its axis in the longitudinal direction, and the aerosol is sprayed again from the nozzle, so that the holder or the nozzle moves linearly in the longitudinal direction of the porous support. To be adjacent to the filmed part It may be sequentially performed with respect to the film formation region of the porous support.

The preparing of the hydrogen separation membrane module may include: (a) installing a porous support interlocked with a rotatable holder provided in the deposition chamber, (b) maintaining the inside of the deposition chamber at a constant pressure, and (c ) The carrier gas is passed through the flow control means, BaCe _x YM _{1 -x} O ₃ , where M is La, Y, Yb, Ga, Gd, In or Ge, and x is real and 0≤x <1. ), SrCe _x YM _{1 -x} O ₃ , where M is La, Y, Yb, Ga, Gd, In or Ge, x is a real number and 0≤x <1, LaSr _x M _{1 -x} O ₃ (Where M is La, Y, Yb, Ga, Gd, In, or Ge, x is a real number and 0 ≦ x <1), BaCe _x M _{1- x} O ₃ (where x is a real number and 0 < x <1, M is one or more rare earth elements selected from Y, La, Er, Eu, and Gd, BaZr _x M _{1- x} O ₃ (where x is a real number, 0 <x <1, and M is One or more rare earth elements selected from Y, La, Er, Eu, and Gd), BaCe _x Zr _y M _{1 -xy} O ₃ , where x and y are real and 0 < x <1, 0 <y <1, 0 <x + y <1, M is at least one rare earth element selected from Y, La, Er, Eu and Gd, SrCe _x M _{1 -x} O ₃ (where x is a real number, 0 <x <1, M is at least one rare earth element selected from Y, La, Er, Eu and Gd) and SrZr _x M _{1- x} O ₃ (where x is a real number and 0 < x <1, M is at least one perovskite oxide powder selected from at least one rare earth element selected from Y, La, Er, Eu, and Gd), and at least one oxide selected from ZnO, NiO, CuO, and CoO Aerosolizing the raw material powder by supplying it to a space where powder is placed; (d) supplying the formed aerosol to a nozzle in the deposition chamber by a pressure difference, and (e) between the nozzle of the nozzle and the porous support to be deposited The aerosol is sprayed toward the porous support while maintaining a constant distance in the range of 2 to 20 mm Forming a hydrogen separation membrane having a mixed conductivity by forming an aerosol sprayed onto the porous support by pulverization by impact, and (f) heat-treating to improve mechanical strength by strengthening interparticle bonding of the hydrogen separation membrane. In the step (e), the aerosol is sprayed from the nozzle so that the porous support is rotated in the longitudinal direction to form a film along the circumferential surface of the porous support, and the circumferential surface of the porous support When the film is formed along the target thickness, the holder or the nozzle is linearly moved in the longitudinal direction of the porous support, and the aerosol is sprayed again from the nozzle to form the film formed by rotating the porous support in the axial direction. Phase with respect to the region of the porous support adjacent to Along the peripheral surface of the porous support may be made of a film-forming.

The preparing of the hydrogen separation membrane module may include: (a) installing a porous support interlocked with a rotatable holder provided in the deposition chamber, (b) maintaining the inside of the deposition chamber at a constant pressure, and (c ) The carrier gas is passed through the flow control means, BaCe _x YM _{1 -x} O ₃ , where M is La, Y, Yb, Ga, Gd, In or Ge, and x is real and 0≤x <1. ), SrCe _x YM _{1 -x} O ₃ , where M is La, Y, Yb, Ga, Gd, In or Ge, x is a real number and 0≤x <1, LaSr _x M _{1 -x} O ₃ (Where M is La, Y, Yb, Ga, Gd, In, or Ge, x is a real number and 0 ≦ x <1), BaCe _x M _{1- x} O ₃ (where x is a real number and 0 < x <1, M is one or more rare earth elements selected from Y, La, Er, Eu, and Gd, BaZr _x M _{1- x} O ₃ (where x is a real number, 0 <x <1, and M is One or more rare earth elements selected from Y, La, Er, Eu, and Gd), BaCe _x Zr _y M _{1 -xy} O ₃ , where x and y are real and 0 < x <1, 0 <y <1, 0 <x + y <1, M is at least one rare earth element selected from Y, La, Er, Eu and Gd, SrCe _x M _{1 -x} O ₃ (where x is a real number, 0 <x <1, M is at least one rare earth element selected from Y, La, Er, Eu and Gd) and SrZr _x M _{1- x} O ₃ (where x is a real number and 0 < x <1, M is at least one perovskite oxide powder selected from at least one rare earth element selected from Y, La, Er, Eu, and Gd), and at least one oxide selected from ZnO, NiO, CuO, and CoO Aerosolizing the raw material powder by supplying it to a space where powder is placed; (d) supplying the formed aerosol to a nozzle in the deposition chamber by a pressure difference, and (e) between the nozzle of the nozzle and the porous support to be deposited The aerosol is sprayed toward the porous support while maintaining a constant distance in the range of 2 to 20 mm Forming a hydrogen separation membrane having a mixed conductivity by forming an aerosol sprayed onto the porous support by pulverization by impact, and (f) heat-treating to improve mechanical strength by strengthening interparticle bonding of the hydrogen separation membrane. In the step (e), as the aerosol is sprayed from the nozzle, the porous support is rotated about its longitudinal axis and the holder or the nozzle is linearly moved in the longitudinal direction of the porous support so that the circle of the porous support is Film formation is simultaneously performed along the main surface and the longitudinal direction, and when the linear movement of the holder or the nozzle reaches the limit, the porous support is moved in the opposite direction to the moved direction, and the porous support is rotated about the axis in the longitudinal direction. This can be done.

According to the present invention, high-purity carbon can be separated from a hydrocarbon-based fuel by direct cracking of a hydrocarbon-based fuel using a hydrogen separation membrane module including a catalyst layer, a hydrogen separation membrane having hydrogen ion conductivity, and a porous support. have.

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

1 to 4 are diagrams for explaining a method of separating carbon from a hydrocarbon (C _x H _y ) -based gas using a hydrogen separation membrane module according to an embodiment of the present invention.
5 is a view illustrating a state in which a second catalyst layer is formed between a porous support and a hydrogen separation membrane and a first catalyst layer is formed on a hydrogen separation membrane as a hydrogen separation membrane module according to another embodiment of the present invention.
6 is a view illustrating a hydrogen separation membrane formed on the outside of the porous support and a catalyst layer formed on the outside of the hydrogen separation membrane as a tubular hydrogen separation membrane module according to another embodiment of the present invention.
FIG. 7 illustrates a tubular hydrogen separation membrane module according to another embodiment of the present invention, in which a second catalyst layer is formed between the porous support and the hydrogen separation membrane and a first catalyst layer is formed outside the hydrogen separation membrane.
FIG. 8 is a view illustrating a hydrogen separation membrane formed inside a porous support and a catalyst layer formed inside the hydrogen separation membrane as a tubular hydrogen separation membrane module according to another embodiment of the present invention.
FIG. 9 illustrates a tubular hydrogen separation membrane module according to another embodiment of the present invention, in which a second catalyst layer is formed between the porous support and the hydrogen separation membrane and a first catalyst layer is formed inside the hydrogen separation membrane.
10 is a view schematically showing an aerosol film-forming apparatus.
FIG. 11 is a view schematically illustrating a case in which a porous support is rotated and linearly moved and an aerosol is sprayed from a nozzle to form a film.
FIG. 12 is a view schematically illustrating a case where an aerosol is sprayed and formed as the porous support rotates and the nozzle moves linearly.
13 is a conceptual diagram schematically showing a deposition apparatus for forming a hydrogen separation membrane module according to a preferred embodiment of the present invention.
14 is a view schematically showing the flux of particles emitted from the target of the deposition apparatus.
15 and 16 are views showing an appearance of a deposition apparatus according to an embodiment of the present invention.
FIG. 17 illustrates a disk type hydrogen separation membrane manufactured according to Experimental Example 1. FIG.
FIG. 18 shows a tubular porous support made of zirconia (ZrO ₂ ).
19 is a photograph showing a hydrogen separation membrane module prepared according to Experimental Example 2.
20 is a graph showing the results of measuring the methane decomposition hydrogen flux (flux) according to the material of the hydrogen separation membrane.
21 is a photograph showing a hydrogen separation membrane module in which a nickel catalyst layer, a hydrogen separation membrane, and a zirconia porous support are formed.
22 is a photograph showing the appearance of carbon remaining on the surface of the nickel (Ni) catalyst layer of the hydrogen separation membrane module.
FIG. 23 is a view showing the results of observing X-ray diffraction patterns by scrubbing and collecting carbon (C) positioned on the surface of a nickel (Ni) catalyst layer.

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 for separating high purity carbon by direct cracking hydrocarbon (C _x H _y ) (where x is a real number equal to or greater than 1 and y is a real number equal to or greater than 2). Hydrogen separation membrane module of the carbon (C _x H _y ) (where x is a real number greater than or equal to 1, y is a real number greater than or equal to 2) decomposition of carbon (C) and hydrogen (H) from the gas The catalyst layer is formed to promote and the hydrogen separation membrane material having hydrogen ion conductivity is coated or deposited on the porous support to improve hydrogen separation characteristics and to desorb carbon. By decomposing a hydrocarbon (C _x H _y ) -based gas, high purity carbon (C) may be produced without generating CO ₂ .

Examples of the hydrocarbon (C _x H _y ) -based gas include gases such as methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), butane (C ₄ H ₁₀ ), and the like. And a carbon (C) -based fuel containing a hydrogen (H) component.

The hydrogen separation membrane module has a catalyst layer for promoting decomposition of carbon (C _x H _y ) -based gas into carbon (C) and hydrogen (H), and a portion having proton (hydrogen ion) conductivity responsible for hydrogen separation. And it includes a porous support for supporting it.

The catalyst layer, the hydrogen separation membrane having a proton conductivity, and the porous support may have various forms for improving hydrogen separation characteristics and various configurations of the system including the separation membrane. Hereinafter, nano size means a nanometer (nm) size, it is used to mean a size in the range of 1 to 1000 nm.

1 to 4 are diagrams for explaining a method of separating carbon from a hydrocarbon (C _x H _y ) -based gas using a hydrogen separation membrane module according to an embodiment of the present invention.

1 to 4, the hydrogen separation membrane module is formed on the porous support 110 and the porous support 110 and has a hydrogen ion conductivity to separate hydrogen from a hydrocarbon-based gas (C _x H _y ). Hydrogen separation membrane 130 discharged to the support 110, and a catalyst layer 140 for promoting the decomposition of carbon (C) and hydrogen (H) from a hydrocarbon (C _x H _y ) -based gas.

When a hydrocarbon (C _x H _y ) -based gas flows into the hydrogen separation membrane module, hydrogen (H ₂ ) is separated while passing through the catalyst layer, the hydrogen separation membrane 130, and the porous support 110, and carbon remains on the surface of the catalyst layer.

Hydrocarbon (C _x H _y ) -based gas flowing into the hydrogen separation membrane module is a high temperature (for example 300 to 900 ℃) and a high pressure (for example 800 to 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 catalyst layer 140 and the hydrogen separation membrane 130 to be decomposed into carbon (C), hydrogen ions (H ⁺ ), and electrons, and the hydrogen ions and electrons are separated from the hydrogen separation membrane ( It is delivered to the porous support 110 through 130, the hydrogen ions and electrons passed through the hydrogen separation membrane 130 is recombination occurs to convert to hydrogen (H ₂ ) is discharged from the porous support 110 do. Hydrogen (H ₂ ) is discharged through the porous support 110 because a myriad of pores exist in the porous support (110). Carbon (C) decomposed from methane (CH ₄ ) is distributed in the catalyst layer 140. When the hydrogen separation membrane module is cooled, high purity carbon may be separated by desorbing carbon (C) positioned on the surface of the catalyst layer 140. Desorption of carbon (C) attached to the surface of the catalyst layer 140 may use a scrubbing method or the like.

The porous support 110 may be formed in a flat plate shape as shown in FIGS. 1 to 5, but as shown in FIGS. 6 to 9, a passage through which hydrogen gas is discharged or a passage through which hydrocarbon-based gas is introduced is provided. The providing tube 120 may be a tubular porous support formed therein. Hereinafter, the inner side means a direction toward the center of the tube on the basis of the porous support, and the outer side means a direction from the center of the tube to the outside on the basis of the porous support.

The size of the porous support 110 may vary depending on the needs, but the pores should be well developed to facilitate the movement of hydrogen gas to the porous support 110. The porous support 110 is formed with a number of pores of 0.1 to 100㎛ size.

Since the hydrogen gas separated by the hydrogen separation membrane 130 should be collected through the porous support 110, the pores formed in the porous support 110 are preferably mainly made of open pores. That is, the porous support 110 in contact with the hydrogen separation membrane 130 is preferably made of pores open from the outer surface of the opposite side of the porous support 110. The pore size formed in the porous support 110 is appropriately 0.1 to 100㎛, more preferably 0.5 to 10㎛. If the size of the pores is excessively large, the strength of the porous support 110 is 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 porous support 110 is suitably 0.1 to 0.7, preferably 0.2 to 0.5 is more suitable. If the porosity (pore volume ratio) of the pores 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 porous support 110 may be made of a material such as SiC, Al ₂ O ₃ , ZrO ₂ , AlTiO ₃ , which is a ceramic material which does not occur deformation at a temperature of 300 to 900 ° C. at which the hydrogen separation membrane module is used.

The pore size may be adjusted by controlling the amount of pore forming agent added to the raw material of the ceramic material and the particle size of the raw material of the ceramic material.

Pore-forming agents, such as organic materials such as tar and carboxymethyl cellulose (CMC), are included in a ceramic material to form many porous pores in the porous 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 porous 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 porous 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 porous support 110 is molded by extrusion, slip casting, or the like. The porous support 110 may be molded in a tubular shape so that a tube (see 120 in FIG. 7) is formed therein. When using an extrusion method, it is preferable to shape | mold so that solid content may reach 70 to 85%, and when using the slip casting method, it is preferable to shape | mold so that solid content may form 30 to 60% range. Extrusion, slip casting, or the like may be used to make the pipe (see 120 of FIG. 7), but may be manufactured in various ways according to desired conditions.

When the porous support 110 is molded, the final porous support 110 is manufactured by baking at a temperature range of 1400 to 1800 ° C. As described above, the pore-forming agent is burned away at a predetermined temperature (eg, 300 ° C. to 600 ° C.) or higher in the firing process, and pores are formed at the burned-out position, and the porous support 110 is porous. .

The hydrogen separation membrane 130 having hydrogen ion conductivity has a porosity of 0.05 or less, preferably a dense membrane, and a thickness of 50 μm or less, preferably 1 to 10 μm. The thicker the thickness, the lower the hydrogen transmittance, resulting in a decrease in the performance of the hydrogen separation membrane 130. When the thickness is excessively thin, the hydrogen separation membrane 130 may not completely cover the pores of the porous support 110 under the hydrogen separation membrane 130, and leakage of the hybrid carbon-based gas may occur. Meanwhile, the hydrogen ion conductivity (logσT) of the hydrogen separation membrane 130 is preferably 0.01 or more when measured at 900 ° C.

The hydrogen separation membrane is BaCe _x YM _{1 -x} O ₃ (wherein M is La, Y, Yb, Ga, Gd, In or Ge, x is real and 0≤x <1), SrCe _x YM _{1 -x} O ₃ , where M is La, Y, Yb, Ga, Gd, In, or Ge, x is a real number and 0 ≦ x <1, LaSr _x M _{1- x} O ₃ , where M is La, Y , Yb, Ga, Gd, In, or Ge, x is a real number and 0 ≦ x <1, BaCe _x M _{1- x} O ₃ , where x is a real number and 0 <x <1, and M is Y , At least one rare earth element selected from La, Er, Eu, and Gd, BaZr _x M _1-x O ₃ , where x is a real number, 0 <x <1, and M is Y, La, Er, Eu, and At least one rare earth element selected from Gd, BaCe _x Zr _y M _{1 -xy} O ₃ (where x and y are real numbers, 0 <x <1, 0 <y <1, 0 <x + y <1) , M is at least one rare earth element selected from Y, La, Er, Eu, and Gd), SrCe _x M _{1 -x} O ₃ (where x is a real number, 0 <x <1, and M is Y, La, Er, Eu, and one or more kinds of rare earth element selected from Gd), SrZr _x M ₁ O _{3 -x} ( , Where, x is a real number, and 0, and <x <1, M may be formed of a perovskite-type material consisting of Y, La, Er, Eu and rare earth elements such as one or more selected from Gd).

The hydrogen separation membrane 130 may be formed on the porous support 110 using 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.

Hydrogen separation membrane 130 is preferably BaCe _x YM _{1 -x} O ₃ (wherein M is La, Y, Yb, Ga, Gd, In or Ge by sputtering method, x is real and 0≤x <1 SrCe _x YM _{1 -x} O ₃ , where M is La, Y, Yb, Ga, Gd, In or Ge, x is a real number and 0≤x <1, and LaSr _x M _{1 -x} O ₃ , where M is La, Y, Yb, Ga, Gd, In or Ge, x is a real number and 0 ≦ x <1, BaCe _x M _1-x O ₃ where x is a real number and 0 <X <1, M is at least one rare earth element selected from Y, La, Er, Eu and Gd), BaZr _x M _{1- x} O ₃ (where x is a real number and 0 <x <1, and M is Is at least one rare earth element selected from Y, La, Er, Eu, and Gd), BaCe _x Zr _y M _{1 -xy} O ₃ (where x and y are real numbers, 0 <x <1, and 0 <y < 1, 0 <x + y <1, M is at least one rare earth element selected from Y, La, Er, Eu and Gd, SrCe _x M _{1- x} O ₃ (where x is a real number and 0 <x < 1, M is at least one selected from Y, La, Er, Eu and Gd Rare earth elements in the phase) and SrZr _x M _{1 -x} O ₃ (where x is a real number, 0 <x <1, and M is one or more rare earth elements selected from Y, La, Er, Eu, and Gd) It can be prepared from the vaporization of the raw material consisting of one or more perovskite-type materials selected from, through which a uniform and dense film can be formed. As an example of the method of manufacturing the hydrogen separation membrane 130, when (unsymmetrical) magnetron sputtering method is used, a membrane having high adhesion to a porous support can be obtained and a low coating process temperature of 300 ° C. or lower is maintained. Because of this, it is possible to have a highly bonded coating that does not deform the physical properties of the substrate (porous support). The hydrogen separation membrane 130 may be manufactured using a raw material having a purity of 99.95% or more composed of a perovskite material in a sealed chamber of a size that can accommodate a desired support. 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 hydrogen separation membrane 130 and the support, an electrode equipped with a permanent magnet is preferably used. In this case, the permanent magnet may be asymmetrically arranged to control the mobility and direction of the deposition material. . The power source used for the deposition of the hydrogen separation membrane 130 is preferably an AC type having a frequency of 1 MHz to 400 MHz or a pulsed DC power source of 5 to 400 KHz. Discharge is generated under a vacuum pressure of 0.01 to 10 mmTorr using an applied power source to form plasma. At this time, Ar or O _{2 is added} to maintain plasma state and to ensure stability of the hydrogen separation layer 130 composition and crystal structure. It is preferable to use within the range of -1,000 ml. The deposition rate of the hydrogen separation film 130 is preferably performed in the range of 0.1 ~ 1 nm / sec. Too fast a deposition rate may lower the adhesion between the deposited hydrogen separation membrane 130 and the porous support, so the deposition rate control as described above is necessary. For uniform deposition of the object, the support is preferably mounted on a rotating shaft connected to the inside or outside of the chamber to rotate at a speed of 1 to 500 rpm. In addition, as another method for ensuring high bonding between the support and the hydrogen separation membrane 130, it is preferable to apply a bias power supply to the support in the range of 1 to 1,000V.

A wet coating method may also be used as a method of forming the hydrogen separation membrane 130. Specifically, the wet coating method may be a dipping method, a slip casting method, or the like. In one example, BaCe _x YM _{1- x} O ₃ , where M is La, Y, Yb, Ga, Gd, In or Ge, x is a real number and 0 ≦ x <1, SrCe _x YM _{1- x} O ₃ , where M is La, Y, Yb, Ga, Gd, In or Ge, x is a real number and 0 ≦ x <1, LaSr _x M _{1- x} O ₃ where M is La, Y, Yb, Ga, Gd, In or Ge, x is a real number and 0≤x <1, BaCe _x M _{1- x} O ₃ (where x is a real number, 0 <x <1, and M is Y, At least one rare earth element selected from La, Er, Eu, and Gd, BaZr _x M _{1 -x} O ₃ , where x is real and 0 <x <1, and M is Y, La, Er, Eu, and Gd At least one rare earth element selected from among others, BaCe _x Zr _y M _{1 -xy} O ₃ (where x and y are real numbers, 0 <x <1, 0 <y <1, 0 <x + y <1, M is one or more rare earth elements selected from Y, La, Er, Eu, and Gd), SrCe _x M _{1 -x} O ₃ (where x is a real number, 0 <x <1, and M is Y, La, Er) At least one rare earth element selected from among Eu, Gd, and SrZr _x M _{1 -x} O ₃ , where x Is a real number, 0 <x <1, and M is selected from the composition of one or more rare earth elements selected from Y, La, Er, Eu, and Gd), and the raw materials converted into respective oxides are mixed, and then a dispersant and a binder are used. The solvent is added to make a slip. In consideration of the densification and porosity of the hydrogen separation membrane 130, the dispersant is preferably added in an amount of 0.1 to 2% by weight based on the total raw materials converted into oxides, and the binder is added to 0.1 to 2% by weight relative to the total raw materials converted into oxides. It is preferable.

Looking at the method of forming the hydrogen separation membrane 130 in detail, first, a perovskite-type oxide is selected, and among the raw material particles converted into the respective oxides, a raw material having an average particle size of 1 μm or less, preferably 0.2 μm or less is used. do. The starting material may be configured differently according to the perovskite-type material to be prepared, for example, BaCO ₃ , CeO ₂ , Y ₂ O ₃ and Gd ₂ to prepare BaCe _0.85 YGd _0.15 O ₃ based perovskite-type material. Starting materials are determined by mixing O ₃ in a molar ratio. 50% by weight of a solvent such as water or alcohol, 0.3% by weight of an acrylic dispersant, and 0.3% by weight of a binder, such as polyvinyl alcohol (PVA), based on an oxide, are mixed with the starting material. To produce a slip. At this time, it is preferable that the solid content of the slip is in the range of about 20 to 50%. The prepared slip is coated on the prepared porous support 110 by slip casting or dipping.

The hydrogen separation membrane 130 may allow the conductive metal nanoparticles or the conductive ceramic nanoparticles having a size of 10 to 200 nm to be contained in the perovskite material in order to further provide electronic conductivity to the hydrogen ion conductivity. the particles may be made of a metal such as a high-Pt, Ni, Pd, Ag, Mo, Fe, Co melting point than a temperature of 300~900 ℃ used hydrogen bunmak body and the ceramic nanoparticles CeO _2, SnO _2, WO ₃ , SiC and the like.

To this end, in order to give electron conductivity to hydrogen ion conductivity, conductive metal nanoparticles or conductive ceramic nanoparticles having a size of 10 to 200 nm may be included in the slip. The conductive metal nanoparticles may be made of at least one metal selected from Pt, Ni, Pd, Ag, Mo, Fe, and Co having a higher melting point than 300 to 900 ° C. at which the hydrogen separation membrane module is used. The ceramic nanoparticles may be made of at least one material selected from CeO ₂ , SnO ₂ , WO ₃ , and SiC. When the metal nanoparticles or ceramic nanoparticles are added together with a material having a perovskite structure and the material of the perovskite structure is sintered, crystal grains are formed, and the metal nasium particles or ceramic nanoparticles are formed between the grains. It has a structure dispersed at the interface. The conductive metal nanoparticles or the conductive ceramic nanoparticles may be deposited together with the hydrogen separation membrane 130 using a sputter deposition apparatus described below.

The hydrogen separation membrane 130 coated or deposited is sintered at 1400 to 1700 ° C. for 30 minutes or more to complete the hydrogen separation membrane 130 capable of hydrogen separation. The porous support 110 may not be sintered before the hydrogen separation membrane 130 is coated. In the present embodiment, the process of forming the hydrogen separation membrane 130 after firing the porous support 110 is described, but after coating the hydrogen separation membrane 130 in a state in which the baking process of the porous support 110 is not performed. In the predetermined process of the hydrogen separation membrane 130, the baking process of the porous support 110 may be performed together. In any case, however, since the hydrogen separation membrane 130 after final sintering should be sufficiently densified and free of gas leakage, it is preferable to use raw materials having a size of 1 μm or less, and raw materials of 0.2 μm or less. More preferably.

Promotes the hydrocarbon (C _x H _y) based gas decomposition reaction of the carbon and hydrogen in the upper hydrogen-separation membrane 130 and form a catalyst layer 140 as shown in Figs. 1 to 4 in order to improve the electronic conductivity . The catalyst layer 140 is preferably composed of at least one or more elements selected from Pt, Ni, Pd, Ag, Mo, and Co.

The catalyst layer 140 formed on the hydrogen separation membrane 130 may be manufactured by various methods. For example, the organic precursor including Pt may be dissolved in a suitable solvent to coat the resulting product having the hydrogen separation membrane 130 formed thereon. can do. The resultant in which the hydrogen separation membrane 130 coated with the organic precursor is formed may be heat-treated to remove organic substances and complete the catalyst layer 140. Heat treatment for the formation of the catalyst layer can be carried out in an air atmosphere at a rate of 2 to 5 ℃ per minute and maintained at 300 to 900 ℃ for 10 minutes to 1 hour and then naturally cooled.

Meanwhile, as shown in FIG. 5, before the hydrogen separation membrane 130 having the hydrogen ion conductivity is coated, the second catalyst layer may be used to promote the recombination reaction between the hydrogen ions and the electrons on the porous support 110 and to improve the electron conductivity. 140a) may be introduced. The second catalyst layer 140a is preferably composed of at least one or more elements selected from Pt, Ni, Pd, Ag, Mo, and Co. The method of forming the second catalyst layer 140a may be performed in the same manner as described above. The second catalyst layer 140a is formed on the porous support 110, the hydrogen separation membrane 130 is formed on the second catalyst layer 140a, and the first catalyst layer 140b is formed on the hydrogen separation membrane 130. Can be. As such, when the second catalyst layer 140a is formed, the recombination reaction between the hydrogen ions and the electrons is promoted, the conductivity of the electrons passing through the hydrogen separation membrane is increased, and the purity of the separated hydrogen gas can be increased, and the first catalyst layer 140a In the case of forming the catalyst, the decomposition reaction of carbon and hydrogen may be promoted, and the conductivity of electrons passing through the hydrogen separation membrane may be increased.

6 is a view showing a hydrogen separation membrane module according to another embodiment of the present invention.

Referring to FIG. 6, the hydrogen separation membrane module has a support body 120 having a porosity therein and a porous body 120 providing a passage through which hydrogen gas is discharged, and a hydrogen support membrane 110 formed at an outer side of the porous support 110. Hydrogen separation membrane 130 which has ion conductivity to separate hydrogen from a hydrocarbon (C _x H _y ) -based gas and is discharged to the porous support 110, and hydrocarbon (C _x H _y ) outside the hydrogen separation membrane 130. It includes a catalyst layer 140 to promote the decomposition reaction of carbon and hydrogen in the system gas and to improve the electron conductivity.

The tube 120 inside the porous support 110 serves as a passage through which hydrogen separated by the hydrogen separation membrane 130 is discharged from an external hydrocarbon (C _x H _y ) -based gas, and the diameter of the tube 120 is It is determined in consideration of the amount of hydrogen gas separated and discharged, and is preferably about 0.5 to 10 cm.

Another example of the present invention shows a tubular hydrogen separation membrane module in FIG.

Referring to FIG. 7, hydrogen ions and electrons recombine in a hydrocarbon (C _x H _y ) -based gas outside the porous support 110 having a tube 120 provided therein for providing a passage through which hydrogen gas is discharged. The second catalyst layer (140a) is formed to promote and improve the electron conductivity, the hydrogen separation membrane 130 having hydrogen ion conductivity is formed on the outer side of the second catalyst layer (140a), the hydrogen separation membrane 130 outer hydrocarbons promote the decomposition reaction of the carbon and hydrogen in the (C _x H _y) based on the gas and there is a first catalyst layer (140b) for improving the electron conductivity is formed. The second catalyst layer 140a may be composed of elements such as Pt, Ni, Pd, Ag, Mo, Co, and the like, and the first catalyst layer 140b is also composed of elements such as Pt, Ni, Pd, Ag, Mo, Co, and the like. The second catalyst layer 140a and the first catalyst layer 140b may be formed of different metals.

As another example of the present invention, a tubular hydrogen separation membrane module is illustrated in FIG. 8.

Referring to FIG. 8, the hydrogen separation membrane module is formed inside the porous support 110 and the porous support 110 in which a tube providing a passage through which a hydrocarbon (C _x H _y ) -based gas is introduced is formed therein. And a hydrogen separation membrane 130 having hydrogen ion conductivity to separate hydrogen from a hydrocarbon (C _x H _y ) -based gas and discharge the hydrogen to the porous support 110, and a hydrocarbon (C _x ) inside the hydrogen separation membrane 130. It includes a catalyst layer 140 for promoting the decomposition reaction of carbon and hydrogen in the H _y- based gas and to improve the electron conductivity. When the catalyst layer is formed inside the hydrogen separation membrane, it may be formed by a wet coating method.

As another example of the present invention, a tubular hydrogen separation membrane module is illustrated in FIG. 9.

Referring to FIG. 9, the hydrogen separation membrane module is formed inside the porous support 110 and the porous support 110 in which a tube providing a passage through which a hydrocarbon (C _x H _y ) -based gas is introduced is formed therein. It is formed inside the second catalyst layer 140a and the second catalyst layer 140a to promote the recombination reaction of hydrogen ions and electrons and to improve the electron conductivity, and has a hydrogen ion conductivity to give hydrocarbon (C _x H _y Hydrogen separation membrane (130) for separating hydrogen from the gas and discharged to the porous support 110, and formed inside the hydrogen separation membrane and promotes the decomposition reaction of carbon and hydrogen in a hydrocarbon (C _x H _y ) gas And a first catalyst layer 140b for improving electron conductivity. The second catalyst layer 140a may be composed of elements such as Pt, Ni, Pd, Ag, Mo, Co, and the like, and the first catalyst layer 140b is also composed of elements such as Pt, Ni, Pd, Ag, Mo, Co, and the like. The second catalyst layer 140a and the first catalyst layer 140b may be formed of different metals.

Although the tubular hydrogen separation membrane module has been described as including the porous support 110, the hydrogen separation membrane 130 and the catalyst layer 140, the hydrogen separation membrane 130 itself is formed in a tubular shape and the catalyst layer ( 140 may be formed.

Hereinafter, a method of manufacturing a hydrogen separation membrane module according to an embodiment of the present invention.

The hydrogen separation membrane module may be formed by coating (depositing) the hydrogen separation membrane on the porous support by the aerosol deposition method using the aerosol deposition apparatus shown in FIG. 10. 10 is a view schematically showing an aerosol film-forming apparatus.

Referring to FIG. 10, 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 step of forming a film while being solidified by an impact on a substrate (porous support 110 in the present invention) which is accelerated by the nozzle 22 and 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 porous 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.

The aerosol film forming apparatus is configured to form a thin film or a thick film by colliding with a porous support 110 at high speed by receiving an aerosol from the aerosol supply portion 10 and aerosol supplying aerosol by floating the raw material powder in a carrier gas A carrier gas supply unit 30 for supplying a carrier gas to the film forming chamber 20, the aerosol supply unit 10, and a pressure control unit 40 for providing a pressure difference between the aerosol supply unit 10 and the film forming chamber 20. ).

The carrier gas supply unit 30 supplies a carrier gas to the aerosol supply unit 10 while controlling the flow rate of the carrier gas through a mass flow controller (MFC) 32, and the carrier gas supply unit 30 and the aerosol supply unit Carrier gas is supplied to the aerosol supply unit 10 through conduits 34 connected between the 10. Conduit 34 is BaCe _x YM _{1- x} O ₃ , raw powder 12, where M is La, Y, Yb, Ga, Gd, In, or Ge, x is real and 0 ≦ x <1 , SrCe _x YM _1-x O ₃ , where M is La, Y, Yb, Ga, Gd, In or Ge, x is a real number and 0 ≦ x <1, LaSr _x M _{1- x} O ₃ ( Where M is La, Y, Yb, Ga, Gd, In, or Ge, x is a real number and 0 ≦ x <1, BaCe _x M _{1- x} O ₃ , where x is a real number and 0 <x <1, M is at least one rare earth element selected from Y, La, Er, Eu, and Gd), BaZr _x M _{1 -x} O ₃ (where x is a real number, 0 <x <1, and M is Y , At least one rare earth element selected from La, Er, Eu, and Gd), BaCe _x Zr _y M _1-xy O ₃ (where x and y are real, 0 <x <1, and 0 <y <1) , 0 <x + y <1, M is at least one rare earth element selected from Y, La, Er, Eu and Gd, SrCe _x M _{1- x} O ₃ (where x is a real number and 0 <x <1) , M is Y, La, Er, rare-earth elements one or more selected from Eu and Gd), SrZr _x M _{1 - at} least one perovskite oxide powder selected from _x O ₃ (where x is a real number, 0 <x <1, and M is at least one rare earth element selected from Y, La, Er, Eu, and Gd), One or more oxide powders selected from ZnO, NiO, CuO, and CoO or a metal powder composed of at least one metal selected from Pt, Ni, Pd, Ag, Mo, Fe, and Co can be easily suspended by the pressure of the carrier gas. It is preferable that the raw material powder 12 is connected to the lower end where it is piled up. The flow rate of the carrier gas supplied from the carrier gas supply unit 30 is an important factor affecting the deposition state, thickness, density, porosity, etc. of the hydrogen separation membrane formed on the porous support 110.

The aerosol supply unit 10 floats the raw material powder 12 in the carrier gas to form an aerosol, and supplies the aerosol 14 to the deposition chamber 20 through the conduit 16. The aerosol supply unit 10 is provided with a vibrator 18 to vibrate the raw material powder 12 so that the raw material powders 12 do not agglomerate with each other and are allowed to float in the air to form the aerosol 14. .

The aerosol 14 is accelerated through the nozzle 22 of the deposition chamber 20 from the aerosol supply 10 through the conduit 16 to be deposited on the porous support 110 fixed to the holder 24. . The holder 24 may be provided to move left and right or up and down on the same plane, and may move at a constant speed while scanning the left and right or up and down to be deposited on the porous support 110 at a uniform thickness during film formation. . The nozzle 22 is provided with a fine injection hole (not shown) of a predetermined size, the aerosol passing through the injection hole of the nozzle 22 by the pressure difference is formed to form a film by colliding with the porous support 110. The aerosol is also accelerated by the shape of the nozzle 22 injection hole, the internal structure of the nozzle 22 into which the aerosol is introduced, and the like. The distance between the injection port of the nozzle 22 and the porous support 110 becomes an important factor in the film formation state, thickness, density, porosity, and the like of the film to be formed.

The pressure controller 40 controls the pressure of the aerosol supply unit 10 and the deposition chamber 20, and may include a rotary pump 42 and a booster pump 44. .

The perovskite-type oxide powder mentioned above on the porous support and at least one oxide powder selected from ZnO, NiO, CuO, and CoO or Pt, Ni, Pd, Ag, Mo, A hydrogen separation film may be formed by forming a metal powder made of at least one metal selected from Fe and Co.

The BaZr _x M _{1 - x} O ₃ oxide (where x is a real number, 0 <x <1, M is one or more rare earth elements selected from Y, La, Er, Eu and Gd) powder is as follows It can be prepared by. BaZr _x M _{1 - x} O ₃ , an oxide of a perovskite crystal structure, where x is a real number, 0 <x <1, and M is one or more rare earth elements selected from Y, La, Er, Eu, and Gd BaCO ₃ , ZrO ₂ , M ₂ O ₃ (wherein M is one or more rare earth elements selected from Y, La, Er, Eu, and Gd) powders are weighed to achieve the composition. The selected and weighed oxide powders are mixed. The mixing may use a ball mill process, which will be described in detail in a ball milling machine and wet mixing with a solvent such as water and alcohol. The oxide powders are mechanically ground and uniformly mixed by rotating at a constant speed using a ball mill. The balls used for ball milling may use balls made of ceramics such as zirconia, and the balls may be all the same size or may be used with balls having two or more sizes. The size of the balls, the milling time, and the rotation speed per minute of the ball miller are adjusted so as to be crushed to the target particle size. For example, the size of the balls may be set in a range of about 1 mm to 10 mm in consideration of the size of the particles, and the rotational speed of the ball miller may be set in a range of about 50 to 500 rpm. Ball milling is carried out for 1 to 24 hours in consideration of the target particle size and the like. By ball milling, the oxide powders are pulverized into finely sized particles, have a uniform particle size distribution, and are uniformly mixed. The mixed slurry is dried. The drying is preferably performed at a temperature of 60 to 120 캜 for 30 minutes to 12 hours. The dried oxide powders are calcined. It is preferable to perform the said calcination for 30 minutes-about 6 hours at the temperature of about 1000 degreeC-1500 degreeC. The calcination step is carried out by heating up to a calcination temperature at a constant rate (for example, 5 to 50 ° C./min), then maintaining the calcination for a certain time (for example, about 1 hour to 6 hours) and cooling to room temperature. Can be. By the calcination process, BaZr _x M _{1 - x} O ₃ oxide (where x is real, 0 <x <1, M is at least one rare earth element selected from Y, La, Er, Eu and Gd) A perovskite oxide powder is formed.

Wherein BaCe _x Zr _y M _{1 -x- y} O ₃ oxide (wherein, x, y is a real number, and 0 <x <1, 0 <y is <1, 0, and <x + y <1, and M is Y, La At least one rare earth element powder selected from among Er, Eu, and Gd is BaCe _x Zr _y M _{1 -xy} O _{3 having a} perovskite crystal structure, where x and y are real and 0 <x <1, 0 <y <1, 0 <x + y <1, and M is at least one rare earth element selected from Y, La, Er, Eu, and Gd) to form a BaCO ₃ , CeO ₂ , ZrO ₂ , M ₂ O ₃ , wherein , M is at least one rare earth element powder selected from Y, La, Er, Eu and Gd, weighed and selected and mixed with the weighed oxide powders, and then BaZr _x M _{1 -x} O ₃ oxide (where , x is a real number, 0 <x <1, M is the same method as the production method of at least one rare earth element powder selected from Y, La, Er, Eu and Gd) BaCe _x Zr _y M _{1 -xy} O ₃ Oxides where x and y are real and 0 &lt; x &lt; 0 <y <1, 0 <x + y <1, and M can form a perovskite oxide powder composed of one or more rare earth elements selected from Y, La, Er, Eu, and Gd.

The SrZr _x M _{1 - x} O ₃ oxide (where x is a real number, 0 <x <1, M is one or more rare earth elements selected from Y, La, Er, Eu and Gd) powder is perovskite SrZr _x M _{1 -x} O ₃ (where x is a real number, 0 <x <1, and M is one or more rare earth elements selected from Y, La, Er, Eu, and Gd) of the crystal structure to form SrCO ₃ , ZrO ₂ , M ₂ O ₃ (wherein M is one or more rare earth elements selected from Y, La, Er, Eu, and Gd) powders are selected and weighed and mixed with selected weighed oxide powders, followed by BaZr _x SrZr in the same manner as in the preparation of M _{1 - x} O ₃ oxide (where x is a real number, 0 <x <1, and M is one or more rare earth elements selected from Y, La, Er, Eu and Gd) powder _x M _{1 - x} O ₃ oxides consisting of (where, x is a real number a, 0 <x <1, and, M is Y, La, Er, 1 or more rare earth elements selected from Eu and Gd) Fe lobe Scar Teuhyeong can form an oxide powder.

The metal powder composed of at least one oxide powder selected from ZnO, NiO, CuO, and CoO or at least one metal selected from Pt, Ni, Pd, Ag, Mo, Fe, and Co forms a dense film of perovskite oxide powder. It helps to lower the sintering temperature. In general, _{BaZr x M 1 - x O 3} , BaCe x Zr y M 1 -x- y O 3 or _{SrZr x M 1 - x O 3} ( where, x, y is a real number and 0 <x <1, 0 <Y <1, 0 <x + y <1, M is at least one rare earth element) oxide selected from Y, La, Er, Eu, and Gd. The sintering should be performed at a high temperature of 1700 ° C., but sintering at a high temperature of 1700 ° C. When the pores formed on the porous support are closed, there is a problem in that hydrogen separation efficiency is lowered, but at least one oxide powder selected from ZnO, NiO, CuO, and CoO or Pt, Ni, Pd, Ag, Mo, Fe, and Co By adding together a metal powder composed of at least one selected metal to form a hydrogen separation membrane, there is an advantage that the sintering can be made even in the range of 1300 ~ 1500 ℃, thereby suppressing the problem of closing the pores formed in the porous support hydrogen separation Inefficiency It can seonhal. The metal powder consisting of at least one oxide powder selected from ZnO, NiO, CuO, and CoO or at least one metal selected from Pt, Ni, Pd, Ag, Mo, Fe, and Co is dissolved in a perovskite oxide powder It helps to form a membrane but does not reduce the conductivity of hydrogen ions. The metal powder consisting of at least one oxide powder selected from ZnO, NiO, CuO, and CoO or at least one metal selected from Pt, Ni, Pd, Ag, Mo, Fe, and Co may be used in 100 parts by weight of a perovskite oxide powder. 0.01 to 5 parts by weight, more preferably 1 to 2 parts by weight is added.

Hereinafter, the perovskite-type oxide powder, which is a raw material powder, on the porous support and the at least one oxide powder selected from ZnO, NiO, CuO, and CoO or Pt, Ni, Pd, Ag using the aerosol film forming apparatus shown in FIG. 10. A method of forming a hydrogen separation membrane by forming a film using a metal powder made of at least one metal selected from among Mo, Fe, and Co will be described.

First, a metal made of a perovskite oxide powder, which is a raw material powder, and at least one oxide powder selected from ZnO, NiO, CuO, and CoO or at least one metal selected from Pt, Ni, Pd, Ag, Mo, Fe, and Co. Prepare a powder, the metal powder consisting of at least one oxide powder selected from the ZnO, NiO, CuO and CoO or at least one metal selected from Pt, Ni, Pd, Ag, Mo, Fe and Co is a perovskite oxide It mounts to the aerosol supply part 10 in the ratio containing 0.01-5 weight part with respect to 100 weight part of powder. The perovskite oxide powder is a mixed conductive oxide that can be used as a hydrogen separation membrane, has high electrical conductivity, has excellent chemical durability against moisture and CO ₂ , and also has high selectivity for CO ₂ and hydrogen (H ₂ ). The metal powder consisting of at least one oxide powder selected from ZnO, NiO, CuO and CoO or at least one metal selected from Pt, Ni, Pd, Ag, Mo, Fe and Co is a perovskite oxide powder. It helps to form a dense film. Particle size of the perovskite oxide powder and at least one oxide powder selected from ZnO, NiO, CuO and CoO or at least one metal selected from Pt, Ni, Pd, Ag, Mo, Fe and Co The thickness is preferably in the range of 5 nm to 6 μm, preferably 0.02 to 0.5 μm, in consideration of the film formation state, thickness, density, porosity, and the like of the hydrogen separation membrane to be formed. When the size of the raw powder particles is less than 5 nm, the impact energy is small, so that it is difficult to form the film. When the size of the raw powder particles is larger than 6 μm, hydrogen ion conductivity is used to separate hydrogen from the hydrocarbon (C _x H _y ) -based gas, thereby forming a porous support. Hydrogen separation effect to discharge to 110 may be small.

The vibrator 18 is used to vibrate 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 to 300 rpm.

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 porous 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. Is preferably 250 to 2500 sccm per unit area (mm 2) of the nozzle injection port. 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 membrane is formed by the injection of a strong aerosol, it is difficult to obtain a hydrogen separation membrane having a 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) It is preferable to maintain the pressure inside the vacuum at a constant pressure (for example, about 1 to 760 torr).

When the pressure of 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 porous support 110. To be. The aerosol 14 sprayed on the porous support 110 is solidified by the impact to form a hydrogen separation membrane. It is preferable that the distance between the injection hole of the nozzle 22 and the porous support 110 is about 2-20 mm. If the distance between the injection port of the nozzle 22 and the porous support 110 is less than 2mm, it is difficult to form a uniform membrane due to the impact energy of the aerosol is too strong, if the distance exceeds 20mm, the density is low Hydrogen separation membrane may be formed.

Since the aerosol 14 sprays the aerosol 14 in a predetermined direction, the holder 24 for fixing the porous support 110 according to the area (or size of the porous support) to form the hydrogen separation membrane is rotated. This makes it possible to scan and form a film of uniform thickness over the entire area during film formation. In order to form a uniform film on the porous support 110, the porous 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 porous support 110 also rotates in association with the rotation of the holder 24. do.

A method of forming a film on the porous 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 porous support 110 (in the direction of the straight arrows in FIGS. 11 and 12) so that the length of the porous support 110 can be obtained. When the film formation is performed sequentially along the direction, and the film formation of the target thickness is formed along the longitudinal direction of the porous support 110, the porous support 110 is rotated about the longitudinal axis (round curves in FIGS. 11 and 12). 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 porous support 110 so that the porous support 110 is adjacent to the deposited portion. 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 porous 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 porous 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 porous support 110, the aerosol is sprayed from the nozzle 22 so that the porous support 110 is rotated in the longitudinal direction axis to form a film sequentially along the circumferential surface of the porous support 110 When the film having a target thickness is formed along the circumferential surface of the porous support 110, the holder 24 or the nozzle 22 is linearly moved in the longitudinal direction of the porous support 110, and at the nozzle 22. As the aerosol is sprayed again, the porous support 110 is rotated about its longitudinal direction to form a film along the circumferential surface of the porous support 110 with respect to the region of the porous support 110 adjacent to the formed portion. By repeating the above process, the raw material powder 12 may be deposited on the porous support 110.

Looking at another method of forming a film on the porous support 110, the aerosol is injected from the nozzle 22 to cause the porous support 110 to rotate in the longitudinal axis and the holder 24 or the nozzle 22 is a porous support ( The film is formed simultaneously along the circumferential surface and the longitudinal direction of the porous support 110 by the 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 porous 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 porous support 110. The film is formed on the porous support 110 while the porous support 110 rotates and moves linearly at the same time.

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

Hydrogen separation membrane prepared according to a preferred embodiment of the present invention is sintered by performing a heat treatment to strengthen the bond between the particles. When the hydrogen separation membrane formed by the aerosol film formation method is sintered, it is possible to have more excellent mechanical strength by interparticle bonding. The heat treatment is preferably performed at a temperature of about 1300 ° C to 1500 ° C for about 1 minute to 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 (1300 ° 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.

On the other hand, the conductive oxide constituting the hydrogen separation membrane has a very low electronic conductivity compared to the ionic conductivity, which requires complexation with a metal, and thus a new method of deposition capable of simultaneously depositing ceramic and metal. The apparatus can be used to form a hydrogen separation membrane.

FIG. 13 is a conceptual view schematically showing a sputter deposition apparatus for forming a hydrogen separation membrane module according to a preferred embodiment of the present invention, FIG. 14 is a view schematically showing the flux of particles emitted from a target of the deposition apparatus, FIG. 15. And FIG. 16 is a view illustrating an appearance of a deposition apparatus according to an embodiment of the present invention.

13 to 16, a deposition apparatus for forming a hydrogen separation membrane module forms a plasma around a target made of a material to be deposited on a porous support disposed in a deposition chamber, and removes a plasma from the target by ion bombardment. A device that allows a material to be released to be deposited on a porous 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 porous support is coated on the surface of the porous support.

In the deposition apparatus for forming the hydrogen separation membrane module, the porous support 110 shown in FIG. 13 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 porous support 110 may be provided to be able to rotate, and may also be provided to be able to rotate. The porous support 110 is mounted on the 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 porous support 110 is rotated by the holder 212. Will also rotate in conjunction. 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 porous support. 110 is also interlocked.

Holder 212 is provided to be heated by a heating means (not shown) to be controlled to a predetermined temperature (for example, 300 ~ 600 ℃). The hydrogen separation membrane is deposited and formed by heating the temperature of the holder 212 to a predetermined temperature (for example, 300 to 600 ° C.) using a heating means to deposit the porous support 110 at a predetermined temperature. It is economical and the process can be simplified because its physical properties are improved and subsequent heat treatment at high temperature is not required.

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 based on the porous support 110, and the angles θ formed by the two targets 220 and 230 are directed to the porous support 110. The flux 232 of the material to be deposited is in the range 90 ° <θ <180 ° in order to reach evenly. The porous support 110 is a region where an area in which the flux 232 of the 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 ( Located in A), the porous support 110 is rotated and revolved in the region A.

The first target 20 includes aluminum (Al), nickel (Ni), titanium (Ti), tantalum (Ta), copper (Cu), molybdenum (Mo), lanthanum (La), yttrium (Y), and europium (Eu). ), A metal or a metal alloy such as gadolinium (Gd), indium (In), gallium (Ga) may be mounted, and the second target 230 may include BaCe _x YM _{1 -x} O ₃ (where M is La, Y, Yb, Ga, Gd, In or Ge, x is a real number and 0≤x <1, SrCe _x YM _{1- x} O ₃ , where M is La, Y, Yb, Ga, Gd, In or Ge, x is a real number and 0≤x <1, LaSr _x M _{1- x} O ₃ , where M is La, Y, Yb, Ga, Gd, In or Ge, x is a real number and 0≤x <C1>, BaCe _x M _{1- x} O ₃ (where x is a real number, 0 <x <1, M is at least one rare earth element selected from Y, La, Er, Eu, and Gd), BaZr _x M _{1 -x} O ₃ (where x is a real number, 0 <x <1, M is one or more rare earth elements selected from Y, La, Er, Eu, and Gd), BaCe _x Zr _y M _{1 -xy} O ₃ (where x and y are real numbers, 0 <x <1, 0 <y <1, and 0 <x + y <1 M is at least one rare earth element selected from Y, La, Er, Eu and Gd, SrCe _x M _1-x O ₃ (where x is a real number and 0 <x <1, and M is Y, La , At least one rare earth element selected from Er, Eu, and Gd, SrZr _x M _{1 -x} O ₃ (where x is a real number, 0 <x <1, and M is selected from Y, La, Er, Eu, and Gd) At least one rare earth element selected), SiC, ZrO ₂ , Al ₂ O ₂ , CeO ₂ , BaCO ₃ , Y ₂ O ₃ , La ₂ O ₃ , Eu ₂ O ₃ , Gd ₂ O ₃ , ZnO, NiO, CoO, Ceramic material such as CuO may be mounted.

The first target 220 is connected to the first power supply unit 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 to the second power supply unit 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. Therefore, the strength of the 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 porous support 110 may be used. It is possible to control the film quality deposited on the surface.

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 to form a composite film made of three or more materials on the porous support 110. 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. The metal or metal alloy particles mounted on the first target 220 and the ceramic material particles mounted on the second target 230 may collide with the first target 220 and the second target 230 with considerable energy. Sputtered from the target 220 and the second target 230.

The sputtered material 225, 235 is incident on the porous support 110 to be deposited. Since the porous support 110 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, DC power is applied to the first target 220 to cause the metal or metal alloy particles to be sputtered from the first target 220, and then a pulse voltage is applied to the second target 230 so that the ceramic material particles are the second target. Sputtering from 230 may cause deposition to be carried out in such a way that metal or metal alloy particles are deposited first on the porous support 110 and ceramic material particles are deposited later, and vice versa. The ceramic material particles are sputtered from the second target 230 by applying a pulse voltage thereto, and then DC power is applied to the first target 220 to sputter the metal or metal alloy particles from the first target 220. The ceramic material particles may be deposited on the support 110 first, and then the deposition may be performed in a manner that allows the metal or metal alloy particles to be deposited later. The DC power is applied to the 220 and the pulse voltage is applied to the second target 230 so that the ceramic material particles and the metal or metal alloy particles may be simultaneously deposited on the porous support 110.

In order to form the above-described hydrogen separation membrane, the following experiment was conducted.

<Experimental Example 1>

BaZrO ₃ powder and Pd powder as raw material powders were prepared and mounted in the aerosol supply unit 10 of the aerosol film-forming apparatus. The BaZrO ₃ powder was used having a particle size of 0.3 ~ 6㎛, the Pd powder was used having a particle size of 0.1 ~ 3㎛. The raw material powder was subjected to an experiment containing 95% by weight of BaZrO ₃ powder and 5% by weight of Pd powder.

BaZrO ₃ powder and Pd powder were vibrated using the vibrator 18 so that the flocculation between the raw 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 BaZrO ₃ powder and the Pd powder were 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 film formation type formed according to the flow rate of the carrier gas will be described in detail below.

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 kept at a vacuum degree of ˜760 torr.

When the pressure of the film forming chamber 20 is formed, a desired film forming condition is formed, the aerosol 14 is supplied from the aerosol supply unit 10 to the nozzle 22 of the film forming chamber 20 to form a porous support (ZrO ₂ ). Film was formed to be sprayed toward 110). The distance between the injection port of the nozzle 22 and the porous support 110 was about 1.5 cm. The aerosol sprayed on the porous support 110 is formed while being pulverized by the impact to form a film.

In the method of forming a film on the porous support 110, the porous 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. When the film is formed on the porous support 110 in a predetermined area while moving in the longitudinal direction of the porous support 110, and the film is formed in a predetermined area along the longitudinal direction of the porous support 110, the holder is rotatable. The holder 240 is moved in the longitudinal direction of the porous support 110 while the porous support 110 is rotated about its longitudinal axis through the 24, and the aerosol 14 is sprayed again from the nozzle 22. The deposition was performed on the region of the porous support 110 adjacent to the formed portion.

At this time, the scan speed of the holder 24 was set to about 10 mm / min to form a uniform thickness over the entire area of the porous support 110 during the film formation, the film formation was carried out at room temperature.

Heat treatment was performed to enhance the interparticle bonding. When the hydrogen separation membrane formed by the aerosol deposition method is heat-treated, it is possible to have more excellent mechanical strength by interparticle bonding. The heat treatment was carried out for 2 hours at a temperature of 1400 ℃, it was carried out by cooling to room temperature.

FIG. 17 illustrates a disk type hydrogen separation membrane manufactured according to Experimental Example 1. FIG.

<Experimental Example 2>

A tubular porous support 110 made of zirconia (ZrO ₂ ) as shown in FIG. 18 is disposed in the deposition chamber 200 of the deposition apparatus for forming a tubular hydrogen separation membrane module, and the tubular porous support 110 is 25 sec. It rotates at / cycle and idles at 35sec / 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 ° so that the flux 232 of the material to be deposited to the tubular porous support 110 can be evenly reached. The tubular porous support 110 has a region in which the flux 232 of the particles sputtered from the first target 220 is distributed and a region in which the flux 232 of the particles sputtered from the second target 230 is distributed. Located in the overlapping area A, the tubular porous support 110 allowed for rotation and revolution in the area A.

Paradium (Pd) was mounted on the first target 220, BaZrO ₃ was mounted on the second target 230, and a DC voltage of 0.4 V was applied to the first target 220 through the first power supply 240. The power is supplied, and the pulse voltage is 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 tubular matrix (110) 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 second target 230 of nickel (Ni) metal particles formed on the first target 220 by colliding with positive energy in the plasma state with the positive targets of the first target 220 and the second target 230. BaZrO ₃ particles attached thereto were sputtered from the first target 220 and the second target 230.

The sputtered materials 225 and 235 were incident on the tubular porous support 110 to allow deposition. As described above, palladium (Pd) metal particles and BaZrO ₃ particles are simultaneously deposited on the tubular porous support 110 by applying DC power to the first target 220 and applying a pulse voltage to the second target 230. In this case, the tubular porous support 110 allowed to rotate and revolve so that the particles sputtered from the first target 220 and the second target 230 are deposited. The temperature of the holder 212 was heated to 400 ° C. (673K) using a heating means to maintain the temperature of the tubular porous support 110 at about 400 ° C., thereby allowing deposition.

19 is a photograph showing a hydrogen separation membrane prepared according to Experimental Example 2.

<Experimental Example 3>

Zirconia BaCe _{0 .9} of 15㎜ × 15㎜ × 0.005㎜ a porous support composed of disc-type with M _{0 .1} O ₃ (where, M is Y, YGa, YIn, YLa and YYb Im) to form an oxide, and hydrogen The methane decomposition hydrogen flux according to the material of the separator was measured and shown in FIG. 20 and Table 1 below.

BCY BCYGa BCYIn BCYLa BCYYb Filtration efficiency 99.7 99.7 99.4 99.8 99.7 Filtration amount
(L / ㎠h)
Room temperature 0 0 0 0 0 800 ℃ 1.12 2.04 1.54 2.18 1.72

20 and in Table 1 is BCY BaCe _{0 .9 0 .1} Y represents O _3, and BCYGa means _{BaCe 0 .9 (YGa) 0.1 O} 3 and, BCYYb is _{BaCe 0 .9 (YYb) 0.1 O} 3 and a means, BCYIn is BaCe _{0 .9} (YIn) mean _0.1 O ₃ and, BCYLa means a _{BaCe 0 .9 (YLa) 0.1 O} 3.

20 and Table 1, the hydrogen obtained through the hydrogen separation membrane module had a high purity of 99.99%. BCYLa showed the best flux performance.

<Experimental Example 4>

A hydrogen separation membrane containing 95 wt% of BaZrO ₃ and 5 wt% of Pd powder was formed on a disk-type porous support made of zirconia, and a nickel (Ni) catalyst layer was formed on the hydrogen separation membrane to prepare a hydrogen separation membrane module. 21 is a photograph showing a hydrogen separation membrane module.

Methane (CH ₄ ) was made at 800 ° C. and 3 atm, and introduced into the hydrogen separation membrane module while purging with argon (Ar) gas for 1 hour at a flow rate of 100 sccm. 22 is a photograph showing that carbon is present on the surface of the nickel (Ni) catalyst layer of the cooled hydrogen separation membrane module.

Comparing FIG. 21 with FIG. 22, it can be seen that the surface of the nickel (Ni) catalyst layer is blackened by carbon (C).

Carbon (C) present on the surface of the nickel (Ni) catalyst layer was collected by scrubbing, and the X-ray diffraction pattern was observed and shown in FIG. 23. As shown in FIG. 23, the powder collected from the nickel (Ni) catalyst layer was confirmed to be carbon (C).

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 portion 12: oxide 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: porous support 120: tube
130: hydrogen separation membrane 140: catalyst layer
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 (5)

Preparing a hydrogen separation membrane module by forming a hydrogen separation membrane having a hydrogen ion conductivity and a catalyst layer on the porous support;
Making a hydrocarbon (C _x H _y ), where x is a real number greater than or equal to 1 and y is a real number greater than or equal to 2, at a pressure of 300 to 900 ° C. and higher than atmospheric pressure;
The hydrocarbon (C _x H _y ) (where x is a real number greater than or equal to 1 and y is a real number greater than or equal to 2) is a catalyst layer, a hydrogen separation membrane having hydrogen ion conductivity, and a hydrogen including a porous support. Introducing into the membrane module;
The hydrocarbon (C _x H _y ) (where x is a real number greater than or equal to 1 and y is a real number greater than or equal to 2) is decomposed into carbon (C) and hydrogen (H) while passing through the catalyst layer. Is promoted, the hydrogen is decomposed into hydrogen ions and electrons while passing through the hydrogen separation membrane, the hydrogen ions and electrons are transferred to the porous support through the hydrogen separation membrane, and the hydrogen ions and electrons pass through the porous support. Recombined and discharged into hydrogen (H ₂ ) gas;
Cooling the hydrogen separation membrane module; And
Desorbing carbon (C) located on the surface of the catalyst layer,
Preparing the hydrogen separation membrane module,
(a) installing a porous support in cooperation with a rotatable holder provided in the deposition chamber;
(b) maintaining the inside of the deposition chamber at a constant pressure;
(c) conveying the carrier gas through the flow control means BaCe _x YM _{1 -x} O ₃ , where M is La, Y, Yb, Ga, Gd, In or Ge, x being a real number and 0≤x < 1), SrCe _x YM _{1 -x} O ₃ , where M is La, Y, Yb, Ga, Gd, In or Ge, x is a real number and 0≤x <1, and LaSr _x M _{1 -x} O ₃ , where M is La, Y, Yb, Ga, Gd, In or Ge, x is a real number and 0 ≦ x <1, BaCe _x M _1-x O ₃ , where x is a real number, 0 <x <1, M is at least one rare earth element selected from Y, La, Er, Eu and Gd, BaZr _x M _{1- x} O ₃ (where x is a real number and 0 <x <1, M is one or more rare earth elements selected from Y, La, Er, Eu, and Gd), BaCe _x Zr _y M _{1 -xy} O ₃ (where x and y are real numbers, 0 <x <1, and 0 <y <1, 0 <x + y <1, M is at least one rare earth element selected from Y, La, Er, Eu and Gd), SrCe _x M _{1- x} O ₃ (where x is a real number and 0 <x <1, M is at least one selected from Y, La, Er, Eu and Gd Rare earth element) and SrZr _x M _{1 -x} O ₃ (where x is a real number, 0 <x <1, and M is one or more rare earth elements selected from Y, La, Er, Eu, and Gd) Aerosolizing the raw powder by supplying the perovskite oxide powder and at least one oxide powder selected from ZnO, NiO, CuO, and CoO to a space;
(d) supplying the formed aerosol to a nozzle in the deposition chamber by a pressure difference;
(e) while maintaining a constant distance between the nozzle of the nozzle and the porous support to be deposited in the range of 2 to 20 mm, the aerosol is sprayed toward the porous support so that the aerosol sprayed on the porous support is crushed by impact. Film-forming to form a hydrogen separation membrane having mixed conductivity; And
(f) heat treatment to improve mechanical strength by strengthening the interparticle bonding of the hydrogen separation membrane,
In the step (e), as the aerosol is sprayed from the nozzle, the holder or the nozzle is linearly moved in the longitudinal direction of the porous support so that film formation is sequentially performed along the longitudinal direction of the porous support, and the porous support When a film having a target thickness is formed along a length direction of the porous support, the porous support is rotated axially in the longitudinal direction, and the aerosol is injected from the nozzle again so that the holder or the nozzle is linearly moved in the longitudinal direction of the porous support. A method of separating carbon from a hydrocarbon-based gas, characterized in that the deposition is performed sequentially with respect to the area of the porous support adjacent to the deposited portion.
Preparing a hydrogen separation membrane module by forming a hydrogen separation membrane having a hydrogen ion conductivity and a catalyst layer on the porous support;
Making a hydrocarbon (C _x H _y ), where x is a real number greater than or equal to 1 and y is a real number greater than or equal to 2, at a pressure of 300 to 900 ° C. and higher than atmospheric pressure;
The hydrocarbon (C _x H _y ) (where x is a real number greater than or equal to 1 and y is a real number greater than or equal to 2) is a catalyst layer, a hydrogen separation membrane having hydrogen ion conductivity, and a hydrogen including a porous support. Introducing into the membrane module;
The hydrocarbon (C _x H _y ) (where x is a real number greater than or equal to 1 and y is a real number greater than or equal to 2) is decomposed into carbon (C) and hydrogen (H) while passing through the catalyst layer. Is promoted, the hydrogen is decomposed into hydrogen ions and electrons while passing through the hydrogen separation membrane, the hydrogen ions and electrons are transferred to the porous support through the hydrogen separation membrane, and the hydrogen ions and electrons pass through the porous support. Recombined and discharged into hydrogen (H ₂ ) gas;
Cooling the hydrogen separation membrane module; And
Desorbing carbon (C) located on the surface of the catalyst layer,
Preparing the hydrogen separation membrane module,
(a) installing a porous support in cooperation with a rotatable holder provided in the deposition chamber;
(b) maintaining the inside of the deposition chamber at a constant pressure;
(c) conveying the carrier gas through the flow control means BaCe _x YM _{1 -x} O ₃ , where M is La, Y, Yb, Ga, Gd, In or Ge, x being a real number and 0≤x < 1), SrCe _x YM _{1 -x} O ₃ , where M is La, Y, Yb, Ga, Gd, In or Ge, x is a real number and 0≤x <1, and LaSr _x M _{1 -x} O ₃ , where M is La, Y, Yb, Ga, Gd, In or Ge, x is a real number and 0 ≦ x <1, BaCe _x M _1-x O ₃ , where x is a real number, 0 <x <1, M is at least one rare earth element selected from Y, La, Er, Eu and Gd, BaZr _x M _{1- x} O ₃ (where x is a real number and 0 <x <1, M is one or more rare earth elements selected from Y, La, Er, Eu, and Gd), BaCe _x Zr _y M _{1 -xy} O ₃ (where x and y are real numbers, 0 <x <1, and 0 <y <1, 0 <x + y <1, M is at least one rare earth element selected from Y, La, Er, Eu and Gd), SrCe _x M _{1- x} O ₃ (where x is a real number and 0 <x <1, M is at least one selected from Y, La, Er, Eu and Gd Rare earth element) and SrZr _x M _{1 -x} O ₃ (where x is a real number, 0 <x <1, and M is one or more rare earth elements selected from Y, La, Er, Eu, and Gd) Aerosolizing the raw powder by supplying the perovskite oxide powder and at least one oxide powder selected from ZnO, NiO, CuO, and CoO to a space;
(d) supplying the formed aerosol to a nozzle in the deposition chamber by a pressure difference;
(e) while maintaining a constant distance between the nozzle of the nozzle and the porous support to be deposited in the range of 2 to 20 mm, the aerosol is sprayed toward the porous support so that the aerosol sprayed on the porous support is crushed by impact. Film-forming to form a hydrogen separation membrane having mixed conductivity; And
(f) heat treatment to improve mechanical strength by strengthening the interparticle bonding of the hydrogen separation membrane,
In the step (e), as the aerosol is sprayed from the nozzle, the porous support is rotated about an axis in the longitudinal direction so that film formation is sequentially performed along the circumferential surface of the porous support, and along the circumferential surface of the porous support. When a film having a target thickness is formed, the holder or the nozzle is linearly moved in the longitudinal direction of the porous support, and the aerosol is sprayed again from the nozzle so that the porous support is rotated about the length direction to be adjacent to the film formed portion. A method of separating carbon from a hydrocarbon-based gas, characterized in that the film is formed along the circumferential surface of the porous support with respect to the region of the porous support.
Preparing a hydrogen separation membrane module by forming a hydrogen separation membrane having a hydrogen ion conductivity and a catalyst layer on the porous support;
Making a hydrocarbon (C _x H _y ), where x is a real number greater than or equal to 1 and y is a real number greater than or equal to 2, at a pressure of 300 to 900 ° C. and higher than atmospheric pressure;
The hydrocarbon (C _x H _y ) (where x is a real number greater than or equal to 1 and y is a real number greater than or equal to 2) is a catalyst layer, a hydrogen separation membrane having hydrogen ion conductivity, and a hydrogen including a porous support. Introducing into the membrane module;
The hydrocarbon (C _x H _y ) (where x is a real number greater than or equal to 1 and y is a real number greater than or equal to 2) is decomposed into carbon (C) and hydrogen (H) while passing through the catalyst layer. Is promoted, the hydrogen is decomposed into hydrogen ions and electrons while passing through the hydrogen separation membrane, the hydrogen ions and electrons are transferred to the porous support through the hydrogen separation membrane, and the hydrogen ions and electrons pass through the porous support. Recombined and discharged into hydrogen (H ₂ ) gas;
Cooling the hydrogen separation membrane module; And
Desorbing carbon (C) located on the surface of the catalyst layer,
Preparing the hydrogen separation membrane module,
(a) installing a porous support in cooperation with a rotatable holder provided in the deposition chamber;
(b) maintaining the inside of the deposition chamber at a constant pressure;
(c) conveying the carrier gas through the flow control means BaCe _x YM _{1 -x} O ₃ , where M is La, Y, Yb, Ga, Gd, In or Ge, x being a real number and 0≤x < 1), SrCe _x YM _{1 -x} O ₃ , where M is La, Y, Yb, Ga, Gd, In or Ge, x is a real number and 0≤x <1, and LaSr _x M _{1 -x} O ₃ , where M is La, Y, Yb, Ga, Gd, In or Ge, x is a real number and 0 ≦ x <1, BaCe _x M _1-x O ₃ , where x is a real number, 0 <x <1, M is at least one rare earth element selected from Y, La, Er, Eu and Gd, BaZr _x M _{1- x} O ₃ (where x is a real number and 0 <x <1, M is one or more rare earth elements selected from Y, La, Er, Eu, and Gd), BaCe _x Zr _y M _{1 -xy} O ₃ (where x and y are real numbers, 0 <x <1, and 0 <y <1, 0 <x + y <1, M is at least one rare earth element selected from Y, La, Er, Eu and Gd), SrCe _x M _{1- x} O ₃ (where x is a real number and 0 <x <1, M is at least one selected from Y, La, Er, Eu and Gd Rare earth element) and SrZr _x M _{1 -x} O ₃ (where x is a real number, 0 <x <1, and M is one or more rare earth elements selected from Y, La, Er, Eu, and Gd) Aerosolizing the raw powder by supplying the perovskite oxide powder and at least one oxide powder selected from ZnO, NiO, CuO, and CoO to a space;
(d) supplying the formed aerosol to a nozzle in the deposition chamber by a pressure difference;
(e) while maintaining a constant distance between the nozzle of the nozzle and the porous support to be deposited in the range of 2 to 20 mm, the aerosol is sprayed toward the porous support so that the aerosol sprayed on the porous support is crushed by impact. Film-forming to form a hydrogen separation membrane having mixed conductivity; And
(f) heat treatment to improve mechanical strength by strengthening the interparticle bonding of the hydrogen separation membrane,
In the step (e), as the aerosol is injected from the nozzle, the porous support is rotated about the longitudinal axis, and the holder or the nozzle is linearly moved in the longitudinal direction of the porous support and the circumferential surface of the porous support. The film formation is simultaneously performed along the longitudinal direction, and when the linear movement of the holder or the nozzle reaches the limit, the film is formed by rotating the porous support in the axial direction while moving in the opposite direction to the moving direction. Separating carbon from a hydrocarbon-based gas, characterized in that
The gas according to any one of claims 1 to 3, wherein the hydrocarbon (C _x H _y ), where x is a real number greater than or equal to 1 and y is a real number greater than or equal to 2 (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ) and butane (C ₄ H ₁₀ ) is a method for separating carbon from a hydrocarbon-based gas, characterized in that at least one gas.
The method of any one of claims 1 to 3, wherein the pressure above atmospheric pressure is a pressure in the range of 800 to 10,000 torr.

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