WO2015020503A1 - Separation membrane, hydrogen separation membrane including separation membrane, and device including hydrogen separation membrane - Google Patents

Separation membrane, hydrogen separation membrane including separation membrane, and device including hydrogen separation membrane Download PDF

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Publication number
WO2015020503A1
WO2015020503A1 PCT/KR2014/007446 KR2014007446W WO2015020503A1 WO 2015020503 A1 WO2015020503 A1 WO 2015020503A1 KR 2014007446 W KR2014007446 W KR 2014007446W WO 2015020503 A1 WO2015020503 A1 WO 2015020503A1
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Prior art keywords
separation membrane
hydrogen
metal
layer
hydrogen separation
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PCT/KR2014/007446
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French (fr)
Inventor
Hyeon Cheol Park
Kwang Hee Kim
Kyoung-Seok Moon
Jae-Ho Lee
Keunwoo CHO
Eun Seog Cho
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Samsung Electronics Co., Ltd.
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Publication of WO2015020503A1 publication Critical patent/WO2015020503A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12Composite membranes; Ultra-thin membranes
    • B01D69/1216Three or more layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12Composite membranes; Ultra-thin membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D63/00Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/06Tubular membrane modules
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081After-treatment of organic or inorganic membranes
    • B01D67/0083Thermal after-treatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/04Tubular membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02Inorganic material
    • B01D71/022Metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02Inorganic material
    • B01D71/022Metals
    • B01D71/0221Group 4 or 5 metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02Inorganic material
    • B01D71/022Metals
    • B01D71/0223Group 8, 9 or 10 metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/01Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/018Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of a noble metal or a noble metal alloy
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/501Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
    • C01B3/503Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C27/00Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/02Alloys based on vanadium, niobium, or tantalum
    • C22C27/025Alloys based on vanadium, niobium, or tantalum alloys based on vanadium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D2053/221Devices
    • B01D2053/223Devices with hollow tubes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/10Noble metals or compounds thereof
    • B01D2255/102Platinum group metals
    • B01D2255/1021Platinum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/10Noble metals or compounds thereof
    • B01D2255/102Platinum group metals
    • B01D2255/1023Palladium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/10Noble metals or compounds thereof
    • B01D2255/102Platinum group metals
    • B01D2255/1025Rhodium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/10Noble metals or compounds thereof
    • B01D2255/102Platinum group metals
    • B01D2255/1026Ruthenium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/10Noble metals or compounds thereof
    • B01D2255/102Platinum group metals
    • B01D2255/1028Iridium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/10Noble metals or compounds thereof
    • B01D2255/104Silver
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/10Noble metals or compounds thereof
    • B01D2255/106Gold
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/20Metals or compounds thereof
    • B01D2255/207Transition metals
    • B01D2255/20723Vanadium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/20Metals or compounds thereof
    • B01D2255/207Transition metals
    • B01D2255/20761Copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2256/00Main component in the product gas stream after treatment
    • B01D2256/16Hydrogen
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2256/00Main component in the product gas stream after treatment
    • B01D2256/22Carbon dioxide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/10Single element gases other than halogens
    • B01D2257/108Hydrogen
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2325/00Details relating to properties of membranes
    • B01D2325/04Characteristic thickness
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2325/00Details relating to properties of membranes
    • B01D2325/10Catalysts being present on the surface of the membrane or in the pores
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2325/00Details relating to properties of membranes
    • B01D2325/20Specific permeability or cut-off range

Definitions

  • a separation membrane, a hydrogen separation membrane including the same, and "a hydrogen separation device including the hydrogen separation membrane are disclosed.
  • a hydrogen separation membrane selectively separating only hydrogen gas from a gas mixture including hydrogen gas is applied for separating, producing, and refining high purity hydrogen or the like.
  • Most of the world's high purity hydrogen gas is generated using such a separation technology. For example, when methane gas is modified, hydrogen (H 2 ) and carbon dioxide (CO 2 ) gasses are produced.
  • hydrogen (H 2 ) and carbon dioxide (CO 2 ) gasses are produced.
  • high purity hydrogen may be obtained since carbon dioxide is not passed through the separation membrane, and only hydrogen gas is passed.
  • there is a coal gasification reaction where gases such as H 2 and CO 2 and the like are generated through coalification and a WGS (water gas shift) reaction, and only hydrogen gas is separated by passing through a separation membrane such that high purity hydrogen may be generated.
  • the separated hydrogen is used to generate electricity as a high purity energy source or to refine petroleum, or as a raw chemical material (NH 4 , olefin, and the like).
  • the separation membrane since the gas left after separating the hydrogen consists of C0 2 in a high concentration, the separation membrane may be used to remove C0 2 -rich gas through capture and storage.
  • a hydrogen separation membrane As for a hydrogen separation membrane, a polymer, a ceramic, a metal, and the like have been developed, and in particular, a metal hydrogen separation membrane has very high purity hydrogen selectivity and may produce high purity hydrogen. In addition, the high purity hydrogen separated from the metal hydrogen separation membrane may be directly used for a polymer electrolyte fuel cell and the like.
  • One embodiment provides a novel separation membrane including a Group 5-based metal, and having high hydrogen permeability and being capable of preventing it from diffusing into a noble metal catalyst layer or vice versa and thus preventing durability deterioration by nitride-treating the surface of the separation membrane.
  • Another embodiment of the present invention provides a method of manufacturing the separation membrane.
  • Yet another embodiment of the present invention provides a hydrogen separation membrane including the separation membrane.
  • Yet another embodiment of the present invention provides a hydrogen separation device including the hydrogen separation membrane.
  • One embodiment provides a separation membrane including a Group 5- based metal, and a nitride layer formed by nitride-treating the surface of the separation membrane.
  • the separation membrane may include a metal layer including vanadium (V) as the Group 5-based metal, a nitride layer of a metal forming the metal layer which is formed on at least one surface of the metal layer, and a metal catalyst layer having hydrogen dissociation capability which is formed on the nitride layer.
  • V vanadium
  • the metal layer may further include niobium (Nb), tantalum (Ta), or niobium and tantalum as the Group 5-based metal.
  • the separation membrane may include the nitride layer of the metal forming the metal layer which is formed by nitride-treating the surface of the metal layer.
  • the nitride layer of the metal may be a vanadium nitride layer, or a nitride layer of a V-Nb alloy, a nitride layer of a V-Ta alloy, or a nitride layer of a V-Nb-Ta alloy.
  • the nitride layer may be formed on at least one side of the separation membrane.
  • a thickness of the nitride layer may be less than or equal to about 50 nm, for example about 10 to about 40 nm.
  • the nitride-treating may be performed by treating the separation membrane with nitrogen (N 2 ), or a mixed gas of nitrogen (N 2 ) and ammonia (NH 3 ).
  • the metal layer may further include an additional element belonging to any one of Groups 4, 8 to 10, and 14 of the periodic table as well as the Group 5-based metal, which are present as an alloy in the metal layer.
  • the additional element belonging to Groups 4, 8 to 10, and 14 of the periodic table may be Ti, Zr, Hf, Fe, Ni, Ir, Pt, Ge, Si, or a combination thereof.
  • the separation membrane may have a body-centered cubic (BCC) crystal structure due to the Group 5-based metal.
  • BCC body-centered cubic
  • the metal catalyst layer having the hydrogen dissociation capability may include at least one metal selected from Pd, Pt, Ru, Ir, and a combination thereof, or an alloy of the foregoing metal, and at least one selected from Cu, Ag, Au, Rh, and a combination thereof.
  • a hydrogen separation membrane including the separation membrane is provided.
  • the hydrogen separation membrane may have hydrogen solubility (H/M) of about 0.01 to about 0.6 measured under conditions of about a 0.1 to about 1 MPa hydrogen pressure and at about 400 °C.
  • H/M hydrogen solubility
  • the hydrogen separation membrane may have hydrogen solubility (H/M) of about 0.1 to about 0.5 measured under conditions of about 0.7 MPa (corresponding to about 7 bar) and at about 400 °C.
  • H/M hydrogen solubility
  • the hydrogen separation membrane may have hydrogen permeability of about 1.0*10 ⁇ 8 to about 15.0*10 "8 mol/m*s*Pa 1/2 at 400 °C.
  • a hydrogen separation device including the hydrogen separation membrane is provided.
  • the hydrogen separation device may further include a chamber equipped with a supplier for a mixed gas including hydrogen gas and a discharge chamber equipped with a discharger for separated hydrogen gas, wherein the hydrogen separation membrane contacts the chamber on one surface of the hydrogen separation membrane and contacts the discharge chamber on the other surface.
  • the hydrogen separation membrane may be formed in a tubular shape, a cylindrical chamber barrier rib having a larger diameter than that of the tubular hydrogen separation membrane may be formed at the outside of the hydrogen separation membrane, a space between the chamber barrier rib and the hydrogen separation membrane may be formed as a chamber, and the inside of the tubular hydrogen separation membrane may be formed as a discharge chamber where hydrogen is discharged.
  • a method of manufacturing the separation membrane is provided.
  • the method of manufacturing the separation membrane includes heat treating the surface of the metal layer including vanadium (V) as the Group 5- based metal with nitrogen (N 2 ) or a mixed gas of nitrogen (N 2 ) and ammonia (NH 3 ).
  • the heat-treating may be performed at a temperature of about 400 °C to about 1 100 °C.
  • the method of manufacturing the separation membrane may further include coating the surface of the nitride layer formed by the heat-treating with a noble metal catalyst layer.
  • Durability of a separation membrane can be improved by suppressing the formation of an intermetallic phase due to mutual diffusion between a metallic layer and a catalyst layer.
  • FIG. 1 schematically shows the cross-section of a hydrogen separation membrane including a catalyst layer 3 on a conventional metal layer 1 (FIG. 1 (a)) and the cross-section of a hydrogen separation membrane including a catalyst layer 3 having hydrogen dissociation capability on a nitride layer 5 after forming the nitride layer 5 on a metal layer 1 according to one embodiment of the present invention (FIG. 1 (b)).
  • FIG. 2 is a SEM photograph showing the cross-section of a hydrogen separation membrane including a nitride layer (VN) of a vanadium alloy by nitride-treating the surface of a vanadium-based alloy (V-Pt) according to one embodiment.
  • VN nitride layer
  • V-Pt vanadium-based alloy
  • FIG. 3 is an EDX (energy dispersive x-ray analysis) graph respectively showing components of a nitride layer (VN) (c) and a vanadium alloy (V-Pt) metal layer (b) in the separation membrane (a) shown in FIG. 2.
  • FIG. 4 is a graph showing component analysis of a V-lr alloy layer and a Pd catalyst layer formed thereon in a thickness direction through SIMS (secondary ion mass spectroscopy), and specifically, FIG. 4 (a) is a graph showing components of the layer before heat treatment, FIG. 4 (b) is a graph showing components of the layer in a thickness direction after heat treatment at 400 °C for 48 hours, and FIG. 4 (c) is a graph showing components of the separation membrane obtained by heat-retreating the Pd-coated separation membrane at 400 °C for 48 hours after nitride-treating a V-lr alloy layer.
  • FIG. 5 is a schematic view showing a hydrogen separation device according to another embodiment.
  • FIG. 6 is a schematic view showing a hydrogen separation device including a tubular shape separation membrane according to another embodiment.
  • a separation membrane including a Group 5-based metal and a nitride layer formed by nitride-treating the surface of the separation membrane includes a metal layer including vanadium (V) as the Group 5-based metal, a nitride layer of a metal forming the metal layer, which is formed on at least one surface of the metal layer, and a metal catalyst layer having hydrogen dissociation capability, which is formed on the nitride layer.
  • V vanadium
  • the metal layer may further include niobium (Nb), tantalum (Ta), or niobium and tantalum, which are Group 5 metals.
  • the separation membrane may include a vanadium nitride layer, or a nitride layer of a V-Nb alloy, a nitride layer of a V-Ta alloy, or a nitride layer of a V-Nb-Ta alloy formed by nitride-treating the surface of the separation membrane.
  • a palladium (Pd)-based alloy As the metal hydrogen separation membrane selectively separating only hydrogen from the gas mixture including hydrogen, a palladium (Pd)-based alloy has been widely researched.
  • the Pd-based alloy acts as a catalyst in a reaction in which hydrogen molecules are dissociated into hydrogen atoms from the surface, and the hydrogen atoms may dissolve and diffuse through interstices of unit cells due to a face-centered cubic (FCC) crystal structure and are thus selectively separated (O. Hatlevik et al., J. of Separation and Purification Technology, 73, 59-64, 2010).
  • the high price of the noble metal Pd is a limiting factor of commercializing a metal hydrogen separation membrane (in 2012, $585/oz), and the development of an economical material for a hydrogen separation membrane for substituting for Pd is urgently needed.
  • a material using Group 5 elements such as vanadium (V), niobium (Nb), and tantalum (Ta) has been researched as the Pd substitute material.
  • Group 5 elements have a body-centered cubic (BCC) crystal structure, and thus Group 5-based metals have higher hydrogen permeation performance of about 10 times to about 100 times that of pure Pd having a face centered cubic (FCC) crystalline structure.
  • BCC body-centered cubic
  • FCC face centered cubic
  • the Group 5-based metals may permeate hydrogen by coating Pd on the surface thereof at a thickness of several hundred nanometers.
  • a separation membrane includes a Group 5-based metal as a main component, and a nitride layer of the metal formed on the surface thereof as a diffusion barrier layer to prevent mutual diffusion with a Pd-based catalyst layer, in order to solve the problems.
  • a separation membrane according to the embodiment includes a vanadium nitride layer, or a nitride layer of a V-Nb alloy, a nitride layer of a V-Ta alloy, or a nitride layer of a V-Nb-Ta alloy on the surface thereof by nitride- treating the surface of the separation membrane including a Group 5-based metal, specifically V (vanadium), and additionally Nb, Ta, or a combination thereof.
  • the nitride layer may be formed on at least one side of the separation membrane, or both sides of the separation membrane.
  • the nitride layer is formed in a thickness of less than or equal to about 50 nm, for example about 10 to about 40 nm, on the separation membrane, and the separation membrane including an additionally stacked metal catalyst layer having hydrogen dissociation capability on the nitride layer may have sufficient hydrogen permeability of about 4 X 10 "8 mol/m*s*Pa 1/2 .
  • the nitride layer has a thickness of more than about 50 nm, hydrogen is not permeated well.
  • the nitride-treating may be performed by treating the separation membrane with nitrogen (N 2 ) or a mixed gas of nitrogen (N 2 ) and ammonia (NH3).
  • N 2 and NH 3 gases flow at each rate of about 200 seem and about 50 seem, and heat-treating is performed at a high temperature, for example about 400 to about 1100 °C, a nitride layer is formed on the surface of the separation membrane.
  • the metal layer may further include an additional element belonging to any one of Groups 4, 8 to 10, and 14 of the periodic table as well as the Group 5-based metal, which may be present as an alloy in the metal layer.
  • the additional element belonging to any one of Groups 4, 8 to 10, and 14 of the periodic table may be Ti, Zr, Hf, Fe, Ni, Ir, Pt, Ge, Si, or a combination thereof.
  • the nitride layer may include the additional metal.
  • the separation membrane has a body-centered cubic (BCC) crystal structure due to the Group 5 element, and accordingly a hydrogen atom that passes through the nitride layer may diffuse and permeate through interstices between unit cells of a BCC crystal structure of the metal layer including the Group 5 element.
  • BCC body-centered cubic
  • the metal catalyst layer may include at least one selected from Pd, Pt, Ru, Ir, and a combination thereof, or an alloy of the foregoing metal, and at least one selected from Cu, Ag, Au, Rh, and a combination thereof.
  • the separation membrane includes the metal catalyst layer
  • the nitride layer prevents mutual diffusion between the metal catalyst layer and the Group 5-based metal layer, and durability deterioration does not occur after operation at a high temperature.
  • Another embodiment of the present invention provides a hydrogen separation membrane including the separation membrane.
  • the hydrogen separation membrane may have hydrogen solubility (H/M) of about 0.01 to about 0.6 measured under conditions of about a 0.1 MPa to about 1 MPa hydrogen pressure and at about 400 °C.
  • H/M hydrogen solubility
  • the hydrogen separation membrane may have hydrogen solubility (H/M) of about 0.1 to about 0.5 measured under conditions of about 0.7 MPa (corresponding to about 7 bar) and at about 400 °C.
  • H/M hydrogen solubility
  • the hydrogen separation membrane may have hydrogen permeability of about 1.0 ⁇ 10 ⁇ 8 to about 15.0x10 "8 mol/m*s*Pa 1/2 at about 400 °C.
  • a hydrogen separation device including the hydrogen separation membrane is provided.
  • the hydrogen separation device may include a chamber equipped with a supplier for a mixed gas including hydrogen gas and a discharge chamber equipped with a discharger for separated hydrogen gas, wherein the hydrogen separation membrane contacts the chamber on one surface of the hydrogen separation membrane, and contacts the discharge chamber on the other surface.
  • FIG. 5 is a schematic view showing a hydrogen separation device 20 according to one embodiment. If a mixed gas including hydrogen gas is introduced into a chamber 22 through a supplier 21 , only the hydrogen gas of the mixed gas is selectively separated into a discharge chamber 24 through the hydrogen separation membrane 23. The separated hydrogen gas may be recovered through a discharger 25.
  • the hydrogen separation device 20 may further include a recovery unit 26 for recovering a residual gas in the chamber 22, after the hydrogen is separated from the chamber 22.
  • the hydrogen separation device 20 is shown in a simplified form for better comprehension and easier description, and may further include additional constitutional components according to its use.
  • the hydrogen separation membrane may be formed in a tubular shape and may be formed with a cylindrical chamber barrier rib having a larger diameter of the tubular shaped hydrogen separation membrane at the outside of the hydrogen separation membrane, wherein the space between the chamber barrier rib and the hydrogen separation membrane is formed as a space, and the inside of the tubular shaped hydrogen separation membrane may be formed as a chamber for discharging hydrogen.
  • FIG. 6 is a schematic view showing a tubular shaped hydrogen separation device 30 according to another embodiment.
  • the hydrogen separation device 30 may include a tubular shaped hydrogen separation membrane 33, and a cylindrical chamber barrier rib 36 with a larger diameter than that of the tubular shaped hydrogen separation membrane and that is formed on the outside of the hydrogen separation membrane 33.
  • a space between the chamber barrier rib 36 and the hydrogen separation membrane 33 may be formed as a chamber 32, and a discharge chamber 34 for discharging hydrogen is formed inside the tubular shaped hydrogen separation membrane.
  • the chamber 32 may be equipped with a supplier (not shown) of a mixed gas including hydrogen gas, and a recovery unit (not shown) for recovering residual gas after the hydrogen gas is separated.
  • the discharge chamber 34 may be equipped with a discharger (not shown) for the separated hydrogen gas.
  • a method of manufacturing the separation membrane is provided.
  • the method of manufacturing the separation membrane includes heat treating the surface of the metal layer including vanadium (V) as the Group 5- based metal with nitrogen (N2), or a mixed gas of nitrogen (N 2 ) and ammonia (NH 3 ).
  • the heat-treating may be performed at a temperature of about 400 °C to about 1 100 °C.
  • the method of manufacturing the separation membrane may further include coating the surface of the nitride layer formed by the heat-treating with a noble metal catalyst layer.
  • the metal catalyst layer is the same as described above and therefore a detailed description thereof is omitted.
  • Example 1 Manufacture of Separation Membrane on which a Surface Nitride Layer is Formed, and Evaluation Thereof
  • the nitride reaction temperature is controlled so that the nitride layer may have a thickness of 30-40 nm (650 °C, 5 min), 50-100 nm (850 °C, 5 min), and 200-500 nm (1000 °C, 5 min).
  • FIG. 2 is a SEM image showing the cross-section of the nitride layer on the V-Pt alloy surface.
  • FIG. 3 is a graph showing component analysis of the nitride layer (VN) and the V-Pt alloy layer in FIG. 2. As shown from FIG. 3, nitrogen (N) element is found in the nitride layer (VN) (c), while no nitrogen (N) element is found in the V-Pt alloy layer (b).
  • each nitride layer having a different thickness is formed, a Pd layer as a catalyst layer is deposited thereon to be 150 nm to 200 nm thick using a sputtering method, hydrogen pressure is applied at up to 7 bars in the feeding part of the separation membrane, hydrogen permeability of the separation membrane is measured according to the following Equation 1 , and the results are provided in the following Table 1.
  • the hydrogen permeability may be calculated according to the following Equation 1. [Equation 1 ]
  • Equation 1 J is flux, L is a thickness of a separation membrane, ⁇ 2, ⁇ is hydrogen feeding pressure, and PH2,out is hydrogen permeation pressure.
  • the nitride layer is required to have a thickness of less than or equal to 50 nm.
  • the nitride layer has a thickness ranging from 0 to 40 nm, efficient hydrogen permeability is obtained.
  • each element shows a sharply changed concentration on the interface between the two layers before the heat treatment, and as shown in FIG. 4B, the Ir, Pd, and V elements are spread on the interface of the two layers when the separation membrane is heat-treated at 400 °C for 48 hours.
  • the separation membrane having the nitride layer shows no diffusion between the metal layer and Pd, although the nitride layer has a small amount of Pd, as shown in FIG. 4C.
  • the small amount of Pd is observed during the SIMS analysis, since a part of the elements in the Pd layer spreads inside the nitride layer when an ion beam is applied to the Pd layer from the top surface.
  • the nitride layer prevents mutual diffusion of a metal of the vanadium (V) alloy layer and a metal of the metal catalyst layer (Pd).
  • a separation membrane preventing mutual diffusion between a Group 5-based metal and a catalyst layer at a high temperature and having excellent hydrogen permeability without durability deterioration is manufactured by nitride-treating the surface of the separation membrane including the Group 5-based metal to form a nitride layer.

Abstract

Disclosed are a separation membrane including a metal layer including vanadium (V) as a Group 5-based metal, and a nitride layer formed by nitride-treating the surface of the separation membrane, and a metal catalyst layer having hydrogen dissociation capability and being formed on the nitride layer, a hydrogen separation membrane including the separation membrane, a hydrogen separation device including the hydrogen separation membrane, and a method of manufacturing the separation membrane.

Description

[DESCRIPTION] [Invention Title]
SEPARATION MEMBRANE, HYDROGEN SEPARATION MEMBRANE INCLUDING SEPARATION MEMBRANE, AND DEVICE INCLUDING HYDROGEN SEPARATION MEMBRANE
[Technical Field ]
A separation membrane, a hydrogen separation membrane including the same, and" a hydrogen separation device including the hydrogen separation membrane are disclosed.
[ Background Art]
A hydrogen separation membrane selectively separating only hydrogen gas from a gas mixture including hydrogen gas is applied for separating, producing, and refining high purity hydrogen or the like. Most of the world's high purity hydrogen gas is generated using such a separation technology. For example, when methane gas is modified, hydrogen (H2) and carbon dioxide (CO2) gasses are produced. By passing the mixed gas through the hydrogen separation membrane, high purity hydrogen may be obtained since carbon dioxide is not passed through the separation membrane, and only hydrogen gas is passed. As another example, there is a coal gasification reaction where gases such as H2 and CO2 and the like are generated through coalification and a WGS (water gas shift) reaction, and only hydrogen gas is separated by passing through a separation membrane such that high purity hydrogen may be generated. The separated hydrogen is used to generate electricity as a high purity energy source or to refine petroleum, or as a raw chemical material (NH4, olefin, and the like). In addition, since the gas left after separating the hydrogen consists of C02 in a high concentration, the separation membrane may be used to remove C02-rich gas through capture and storage.
As for a hydrogen separation membrane, a polymer, a ceramic, a metal, and the like have been developed, and in particular, a metal hydrogen separation membrane has very high purity hydrogen selectivity and may produce high purity hydrogen. In addition, the high purity hydrogen separated from the metal hydrogen separation membrane may be directly used for a polymer electrolyte fuel cell and the like.
[Disclosure]
[Technical Problem]
One embodiment provides a novel separation membrane including a Group 5-based metal, and having high hydrogen permeability and being capable of preventing it from diffusing into a noble metal catalyst layer or vice versa and thus preventing durability deterioration by nitride-treating the surface of the separation membrane.
Another embodiment of the present invention provides a method of manufacturing the separation membrane.
Yet another embodiment of the present invention provides a hydrogen separation membrane including the separation membrane.
Yet another embodiment of the present invention provides a hydrogen separation device including the hydrogen separation membrane.
[Technical Solution]
One embodiment provides a separation membrane including a Group 5- based metal, and a nitride layer formed by nitride-treating the surface of the separation membrane.
Specifically, the separation membrane may include a metal layer including vanadium (V) as the Group 5-based metal, a nitride layer of a metal forming the metal layer which is formed on at least one surface of the metal layer, and a metal catalyst layer having hydrogen dissociation capability which is formed on the nitride layer.
The metal layer may further include niobium (Nb), tantalum (Ta), or niobium and tantalum as the Group 5-based metal.
The separation membrane may include the nitride layer of the metal forming the metal layer which is formed by nitride-treating the surface of the metal layer.
The nitride layer of the metal may be a vanadium nitride layer, or a nitride layer of a V-Nb alloy, a nitride layer of a V-Ta alloy, or a nitride layer of a V-Nb-Ta alloy.
The nitride layer may be formed on at least one side of the separation membrane.
A thickness of the nitride layer may be less than or equal to about 50 nm, for example about 10 to about 40 nm.
The nitride-treating may be performed by treating the separation membrane with nitrogen (N2), or a mixed gas of nitrogen (N2) and ammonia (NH3).
The metal layer may further include an additional element belonging to any one of Groups 4, 8 to 10, and 14 of the periodic table as well as the Group 5-based metal, which are present as an alloy in the metal layer.
For example, the additional element belonging to Groups 4, 8 to 10, and 14 of the periodic table may be Ti, Zr, Hf, Fe, Ni, Ir, Pt, Ge, Si, or a combination thereof.
The separation membrane may have a body-centered cubic (BCC) crystal structure due to the Group 5-based metal.
The metal catalyst layer having the hydrogen dissociation capability may include at least one metal selected from Pd, Pt, Ru, Ir, and a combination thereof, or an alloy of the foregoing metal, and at least one selected from Cu, Ag, Au, Rh, and a combination thereof.
According to another embodiment of the present invention, a hydrogen separation membrane including the separation membrane is provided.
The hydrogen separation membrane may have hydrogen solubility (H/M) of about 0.01 to about 0.6 measured under conditions of about a 0.1 to about 1 MPa hydrogen pressure and at about 400 °C.
The hydrogen separation membrane may have hydrogen solubility (H/M) of about 0.1 to about 0.5 measured under conditions of about 0.7 MPa (corresponding to about 7 bar) and at about 400 °C.
In one embodiment, the hydrogen separation membrane may have hydrogen permeability of about 1.0*10~8 to about 15.0*10"8 mol/m*s*Pa1/2 at 400 °C.
According to yet another embodiment of the present invention, a hydrogen separation device including the hydrogen separation membrane is provided.
The hydrogen separation device may further include a chamber equipped with a supplier for a mixed gas including hydrogen gas and a discharge chamber equipped with a discharger for separated hydrogen gas, wherein the hydrogen separation membrane contacts the chamber on one surface of the hydrogen separation membrane and contacts the discharge chamber on the other surface.
In an exemplary embodiment, the hydrogen separation membrane may be formed in a tubular shape, a cylindrical chamber barrier rib having a larger diameter than that of the tubular hydrogen separation membrane may be formed at the outside of the hydrogen separation membrane, a space between the chamber barrier rib and the hydrogen separation membrane may be formed as a chamber, and the inside of the tubular hydrogen separation membrane may be formed as a discharge chamber where hydrogen is discharged.
According to still another embodiment of the present invention, a method of manufacturing the separation membrane is provided.
The method of manufacturing the separation membrane includes heat treating the surface of the metal layer including vanadium (V) as the Group 5- based metal with nitrogen (N2) or a mixed gas of nitrogen (N2) and ammonia (NH3). The heat-treating may be performed at a temperature of about 400 °C to about 1 100 °C.
The method of manufacturing the separation membrane may further include coating the surface of the nitride layer formed by the heat-treating with a noble metal catalyst layer.
[Advantageous Effects]
Durability of a separation membrane can be improved by suppressing the formation of an intermetallic phase due to mutual diffusion between a metallic layer and a catalyst layer.
[Description of Drawings]
FIG. 1 schematically shows the cross-section of a hydrogen separation membrane including a catalyst layer 3 on a conventional metal layer 1 (FIG. 1 (a)) and the cross-section of a hydrogen separation membrane including a catalyst layer 3 having hydrogen dissociation capability on a nitride layer 5 after forming the nitride layer 5 on a metal layer 1 according to one embodiment of the present invention (FIG. 1 (b)).
FIG. 2 is a SEM photograph showing the cross-section of a hydrogen separation membrane including a nitride layer (VN) of a vanadium alloy by nitride-treating the surface of a vanadium-based alloy (V-Pt) according to one embodiment.
FIG. 3 is an EDX (energy dispersive x-ray analysis) graph respectively showing components of a nitride layer (VN) (c) and a vanadium alloy (V-Pt) metal layer (b) in the separation membrane (a) shown in FIG. 2. FIG. 4 is a graph showing component analysis of a V-lr alloy layer and a Pd catalyst layer formed thereon in a thickness direction through SIMS (secondary ion mass spectroscopy), and specifically, FIG. 4 (a) is a graph showing components of the layer before heat treatment, FIG. 4 (b) is a graph showing components of the layer in a thickness direction after heat treatment at 400 °C for 48 hours, and FIG. 4 (c) is a graph showing components of the separation membrane obtained by heat-retreating the Pd-coated separation membrane at 400 °C for 48 hours after nitride-treating a V-lr alloy layer.
FIG. 5 is a schematic view showing a hydrogen separation device according to another embodiment.
FIG. 6 is a schematic view showing a hydrogen separation device including a tubular shape separation membrane according to another embodiment.
[Best Mode]
This disclosure will be described more fully hereinafter in the following detailed description, in which some but not all embodiments of this disclosure are described. However, this disclosure may be embodied in many different forms, and is not construed as limited to the exemplary embodiments set forth herein.
As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of this disclosure. The size and thickness of each constituent element as shown in the drawings are randomly indicated for better understanding and ease of description, and this disclosure is not necessarily limited to as shown. The size and thickness of each constituent element as shown in the drawings are exaggeratedly indicated for better understanding and ease of description, and this disclosure is not necessarily limited to as shown.
According to one embodiment of the present invention, a separation membrane including a Group 5-based metal and a nitride layer formed by nitride-treating the surface of the separation membrane is provided. Specifically, the separation membrane includes a metal layer including vanadium (V) as the Group 5-based metal, a nitride layer of a metal forming the metal layer, which is formed on at least one surface of the metal layer, and a metal catalyst layer having hydrogen dissociation capability, which is formed on the nitride layer.
The metal layer may further include niobium (Nb), tantalum (Ta), or niobium and tantalum, which are Group 5 metals.
*
Therefore, the separation membrane may include a vanadium nitride layer, or a nitride layer of a V-Nb alloy, a nitride layer of a V-Ta alloy, or a nitride layer of a V-Nb-Ta alloy formed by nitride-treating the surface of the separation membrane.
As the metal hydrogen separation membrane selectively separating only hydrogen from the gas mixture including hydrogen, a palladium (Pd)-based alloy has been widely researched. The Pd-based alloy acts as a catalyst in a reaction in which hydrogen molecules are dissociated into hydrogen atoms from the surface, and the hydrogen atoms may dissolve and diffuse through interstices of unit cells due to a face-centered cubic (FCC) crystal structure and are thus selectively separated (O. Hatlevik et al., J. of Separation and Purification Technology, 73, 59-64, 2010).
However, the high price of the noble metal Pd is a limiting factor of commercializing a metal hydrogen separation membrane (in 2012, $585/oz), and the development of an economical material for a hydrogen separation membrane for substituting for Pd is urgently needed. Recently, a material using Group 5 elements such as vanadium (V), niobium (Nb), and tantalum (Ta) has been researched as the Pd substitute material.
Group 5 elements have a body-centered cubic (BCC) crystal structure, and thus Group 5-based metals have higher hydrogen permeation performance of about 10 times to about 100 times that of pure Pd having a face centered cubic (FCC) crystalline structure. However, since the Group 5-based metals have no catalyst characteristics for the reaction of dissociating hydrogen molecules into hydrogen atoms, differing from Pd, the Group 5-based metals may permeate hydrogen by coating Pd on the surface thereof at a thickness of several hundred nanometers.
On the other hand, the Pd and Group 5-based metal may form an intermetaliic phase through mutual diffusion at a high temperature, and may cause durability deterioration. Accordingly, in this disclosure, a separation membrane includes a Group 5-based metal as a main component, and a nitride layer of the metal formed on the surface thereof as a diffusion barrier layer to prevent mutual diffusion with a Pd-based catalyst layer, in order to solve the problems.
A separation membrane according to the embodiment includes a vanadium nitride layer, or a nitride layer of a V-Nb alloy, a nitride layer of a V-Ta alloy, or a nitride layer of a V-Nb-Ta alloy on the surface thereof by nitride- treating the surface of the separation membrane including a Group 5-based metal, specifically V (vanadium), and additionally Nb, Ta, or a combination thereof.
The nitride layer may be formed on at least one side of the separation membrane, or both sides of the separation membrane.
The nitride layer is formed in a thickness of less than or equal to about 50 nm, for example about 10 to about 40 nm, on the separation membrane, and the separation membrane including an additionally stacked metal catalyst layer having hydrogen dissociation capability on the nitride layer may have sufficient hydrogen permeability of about 4 X 10"8 mol/m*s*Pa1/2.
However, if the nitride layer has a thickness of more than about 50 nm, hydrogen is not permeated well.
The nitride-treating may be performed by treating the separation membrane with nitrogen (N2) or a mixed gas of nitrogen (N2) and ammonia (NH3). For example, while N2 and NH3 gases flow at each rate of about 200 seem and about 50 seem, and heat-treating is performed at a high temperature, for example about 400 to about 1100 °C, a nitride layer is formed on the surface of the separation membrane.
The metal layer may further include an additional element belonging to any one of Groups 4, 8 to 10, and 14 of the periodic table as well as the Group 5-based metal, which may be present as an alloy in the metal layer.
For example, the additional element belonging to any one of Groups 4, 8 to 10, and 14 of the periodic table may be Ti, Zr, Hf, Fe, Ni, Ir, Pt, Ge, Si, or a combination thereof.
When the separation membrane includes the additional metal as well as the Group 5-based metal, the nitride layer may include the additional metal.
The separation membrane has a body-centered cubic (BCC) crystal structure due to the Group 5 element, and accordingly a hydrogen atom that passes through the nitride layer may diffuse and permeate through interstices between unit cells of a BCC crystal structure of the metal layer including the Group 5 element.
The metal catalyst layer may include at least one selected from Pd, Pt, Ru, Ir, and a combination thereof, or an alloy of the foregoing metal, and at least one selected from Cu, Ag, Au, Rh, and a combination thereof.
Although the separation membrane includes the metal catalyst layer, the nitride layer prevents mutual diffusion between the metal catalyst layer and the Group 5-based metal layer, and durability deterioration does not occur after operation at a high temperature.
Another embodiment of the present invention provides a hydrogen separation membrane including the separation membrane.
The hydrogen separation membrane may have hydrogen solubility (H/M) of about 0.01 to about 0.6 measured under conditions of about a 0.1 MPa to about 1 MPa hydrogen pressure and at about 400 °C.
The hydrogen separation membrane may have hydrogen solubility (H/M) of about 0.1 to about 0.5 measured under conditions of about 0.7 MPa (corresponding to about 7 bar) and at about 400 °C.
In one embodiment, the hydrogen separation membrane may have hydrogen permeability of about 1.0χ10~8 to about 15.0x10"8 mol/m*s*Pa1/2 at about 400 °C.
According to another embodiment, a hydrogen separation device including the hydrogen separation membrane is provided.
The hydrogen separation device may include a chamber equipped with a supplier for a mixed gas including hydrogen gas and a discharge chamber equipped with a discharger for separated hydrogen gas, wherein the hydrogen separation membrane contacts the chamber on one surface of the hydrogen separation membrane, and contacts the discharge chamber on the other surface.
FIG. 5 is a schematic view showing a hydrogen separation device 20 according to one embodiment. If a mixed gas including hydrogen gas is introduced into a chamber 22 through a supplier 21 , only the hydrogen gas of the mixed gas is selectively separated into a discharge chamber 24 through the hydrogen separation membrane 23. The separated hydrogen gas may be recovered through a discharger 25. The hydrogen separation device 20 may further include a recovery unit 26 for recovering a residual gas in the chamber 22, after the hydrogen is separated from the chamber 22. The hydrogen separation device 20 is shown in a simplified form for better comprehension and easier description, and may further include additional constitutional components according to its use.
According to one embodiment, the hydrogen separation membrane may be formed in a tubular shape and may be formed with a cylindrical chamber barrier rib having a larger diameter of the tubular shaped hydrogen separation membrane at the outside of the hydrogen separation membrane, wherein the space between the chamber barrier rib and the hydrogen separation membrane is formed as a space, and the inside of the tubular shaped hydrogen separation membrane may be formed as a chamber for discharging hydrogen.
FIG. 6 is a schematic view showing a tubular shaped hydrogen separation device 30 according to another embodiment. The hydrogen separation device 30 may include a tubular shaped hydrogen separation membrane 33, and a cylindrical chamber barrier rib 36 with a larger diameter than that of the tubular shaped hydrogen separation membrane and that is formed on the outside of the hydrogen separation membrane 33. In this case, a space between the chamber barrier rib 36 and the hydrogen separation membrane 33 may be formed as a chamber 32, and a discharge chamber 34 for discharging hydrogen is formed inside the tubular shaped hydrogen separation membrane. The chamber 32 may be equipped with a supplier (not shown) of a mixed gas including hydrogen gas, and a recovery unit (not shown) for recovering residual gas after the hydrogen gas is separated. Further, the discharge chamber 34 may be equipped with a discharger (not shown) for the separated hydrogen gas.
According to another embodiment, a method of manufacturing the separation membrane is provided.
The method of manufacturing the separation membrane includes heat treating the surface of the metal layer including vanadium (V) as the Group 5- based metal with nitrogen (N2), or a mixed gas of nitrogen (N2) and ammonia (NH3). The heat-treating may be performed at a temperature of about 400 °C to about 1 100 °C.
The method of manufacturing the separation membrane may further include coating the surface of the nitride layer formed by the heat-treating with a noble metal catalyst layer.
The metal catalyst layer is the same as described above and therefore a detailed description thereof is omitted.
Hereinafter, the embodiments are illustrated in more detail with reference to examples. However, they are exemplary examples of the present invention, and this disclosure is not limited thereto.
[Mode for Invention]
Example 1 : Manufacture of Separation Membrane on which a Surface Nitride Layer is Formed, and Evaluation Thereof
A surface nitride layer is formed by heat-treating a V-Pt or V-lr alloy layer for a predetermined time at a high temperature (400-1 100 °C), while a gas (N2:NH3 = 200 sccm:50 seem) flows therein. The nitride reaction temperature is controlled so that the nitride layer may have a thickness of 30-40 nm (650 °C, 5 min), 50-100 nm (850 °C, 5 min), and 200-500 nm (1000 °C, 5 min).
FIG. 2 is a SEM image showing the cross-section of the nitride layer on the V-Pt alloy surface. In addition, FIG. 3 is a graph showing component analysis of the nitride layer (VN) and the V-Pt alloy layer in FIG. 2. As shown from FIG. 3, nitrogen (N) element is found in the nitride layer (VN) (c), while no nitrogen (N) element is found in the V-Pt alloy layer (b).
On the other hand, each nitride layer having a different thickness is formed, a Pd layer as a catalyst layer is deposited thereon to be 150 nm to 200 nm thick using a sputtering method, hydrogen pressure is applied at up to 7 bars in the feeding part of the separation membrane, hydrogen permeability of the separation membrane is measured according to the following Equation 1 , and the results are provided in the following Table 1.
(Table 1 )
The hydrogen permeability may be calculated according to the following Equation 1. [Equation 1 ]
Permeability =
Figure imgf000017_0001
In Equation 1 , J is flux, L is a thickness of a separation membrane, ΡΗ2,ΙΠ is hydrogen feeding pressure, and PH2,out is hydrogen permeation pressure.
Based on the results of Table 1 , the nitride layer is required to have a thickness of less than or equal to 50 nm. When the nitride layer has a thickness ranging from 0 to 40 nm, efficient hydrogen permeability is obtained.
On the other hand, mutual diffusions of a separation membrane having the nitride layer and another separation membrane having no nitride layer are examined at a high temperature by measuring concentration of V, Pd, and Ir elements in a thickness direction before and after heat treatment of the separation membrane including a Pd coating layer on a V-lr separation membrane having no nitride layer and concentrations of V, Pd, Ir, and VN elements in a thickness direction in another separation membrane having a 30 - 40 nm thick nitride layer through SIMS (secondary ion mass spectroscopy) analysis, and the results are respectively provided in FIGS. 4A, 4B, and 4C.
As shown from FIG. 4A, when the separation membrane is coated with a Pd catalyst layer without forming a nitride layer on the surface, each element shows a sharply changed concentration on the interface between the two layers before the heat treatment, and as shown in FIG. 4B, the Ir, Pd, and V elements are spread on the interface of the two layers when the separation membrane is heat-treated at 400 °C for 48 hours.
On the other hand, the separation membrane having the nitride layer shows no diffusion between the metal layer and Pd, although the nitride layer has a small amount of Pd, as shown in FIG. 4C. The small amount of Pd is observed during the SIMS analysis, since a part of the elements in the Pd layer spreads inside the nitride layer when an ion beam is applied to the Pd layer from the top surface. In other words, the nitride layer prevents mutual diffusion of a metal of the vanadium (V) alloy layer and a metal of the metal catalyst layer (Pd).
Based on the results, a separation membrane preventing mutual diffusion between a Group 5-based metal and a catalyst layer at a high temperature and having excellent hydrogen permeability without durability deterioration is manufactured by nitride-treating the surface of the separation membrane including the Group 5-based metal to form a nitride layer. While this disclosure has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

[CLAIMS]
[Claim 1 ]
A separation membrane, comprising:
a metal layer including vanadium (V) as a Group 5-based metal;
a nitride layer of the metal forming the metal layer, which is formed on at least one surface of the metal layer; and
a metal catalyst layer having hydrogen dissociation capability, which is formed on the nitride layer.
[Claim 2]
The separation membrane of claim 1 , wherein the metal layer further comprises niobium (Nb), tantalum (Ta), or niobium and tantalum.
[Claim 3]
The separation membrane of claim 1 , wherein the nitride layer has a thickness of less than or equal to about 50 nm.
[Claim 4]
The separation membrane of claim 1 , wherein the nitride layer has a thickness of about 10 to about 40 nm.
[Claim 5]
The separation membrane of claim 1 , wherein the nitride layer is formed by treating the surface of the metal layer with nitrogen (N2) or a mixed gas of nitrogen (N2) and ammonia (NH3).
[Claim 6]
The separation membrane of claim 1 , wherein the metal layer further comprises an additional element belonging to any one of Groups 4, 8 to 10, and 14 of the periodic table.
[Claim 7]
The separation membrane of claim 6, wherein the additional element belonging to any one of Groups 4, 8 to 10, and 14 of the periodic table is Fe, Ni, Ir, Pt, Ge, Si, or a combination thereof.
[Claim 8]
The separation membrane of claim 7, wherein the additional element belonging to any one of Groups 4, 8 to 10, and 14 of the periodic table is Ir or Pt.
[Claim 9]
The separation membrane of claim 1 , wherein the metal layer of the separation membrane has a body-centered cubic (BCC) crystal structure.
[Claim 10]
The separation membrane of claim 1 , wherein the metal catalyst layer comprises at least one metal selected from Pd, Pt, Ru, Ir, and a combination thereof, or an alloy of the foregoing metal and at least one selected from Cu, Ag, Au, Rh, and a combination thereof.
[Claim 11 ]
A hydrogen separation membrane comprising the separation membrane according to claim 1.
[Claim 12]
The hydrogen separation membrane of claim 11 , wherein the hydrogen separation membrane has hydrogen solubility (H/M) of about 0.01 to about 0.6 measured under conditions of about 0.1 MPa to about 1 MPa of hydrogen pressure and at about 400 °C.
[Claim 13]
The hydrogen separation membrane of claim 11 , wherein the hydrogen separation membrane has hydrogen solubility (H/M) of about 0.1 to about 0.5 measured under conditions of about 0.7 MPa (corresponding to about 7 bar) and at about 400 °C.
[Claim 14]
The hydrogen separation membrane of claim 11 , wherein the hydrogen separation membrane has hydrogen permeability of about 1.0x10"8 to about
15.0*10"8 mol/mVPa1" at 400 °C. [Claim 15]
A hydrogen separation device comprising the hydrogen separation membrane according to claim 11.
[Claim 16]
The hydrogen separation device of claim 15, further including a chamber equipped with a supplier for a mixed gas including hydrogen gas, and
a discharge chamber equipped with a discharger for separated hydrogen gas,
wherein the hydrogen separation membrane contacts the chamber on one surface of the hydrogen separation membrane, and contacts the discharge chamber on the other surface.
[Claim 17]
The hydrogen separation device of claim 16, wherein the hydrogen separation membrane is formed in a tubular shape, a cylindrical chamber barrier rib having a larger diameter than that of the tubular hydrogen separation membrane is formed at the outside of the hydrogen separation membrane, a space between the chamber barrier rib and the hydrogen separation membrane is formed as a chamber, and the inside of the tubular hydrogen separation membrane is formed as a discharge chamber where hydrogen is discharged.
[Claim 18]
A method of manufacturing a separation membrane, comprising heat treating the surface of the metal layer including vanadium (V) as the Group 5- based metal with nitrogen (N2) or a mixed gas of nitrogen (N2) and ammonia (NH3) to manufacture the separation membrane according to claim 1.
[Claim 19]
The method of claim 18, wherein the heat-treating is performed at a temperature of about 400 °C to about 1 100 °C.
[Claim 20]
The method of claim 8, which further comprising coating the surface of the nitride layer formed by the heat-treating with a noble metal catalyst layer having hydrogen dissociation capability.
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