WO2007105594A1 - 水素透過分離薄膜 - Google Patents
水素透過分離薄膜 Download PDFInfo
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- WO2007105594A1 WO2007105594A1 PCT/JP2007/054552 JP2007054552W WO2007105594A1 WO 2007105594 A1 WO2007105594 A1 WO 2007105594A1 JP 2007054552 W JP2007054552 W JP 2007054552W WO 2007105594 A1 WO2007105594 A1 WO 2007105594A1
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- Prior art keywords
- alloy
- hydrogen
- solid solution
- intermetallic compound
- thin film
- Prior art date
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- 239000012528 membrane Substances 0.000 title abstract description 44
- 238000000926 separation method Methods 0.000 title abstract description 13
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 58
- 239000000956 alloy Substances 0.000 claims abstract description 58
- 239000006104 solid solution Substances 0.000 claims abstract description 38
- 229910001000 nickel titanium Inorganic materials 0.000 claims abstract description 37
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 33
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 229910001257 Nb alloy Inorganic materials 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000010419 fine particle Substances 0.000 claims abstract description 13
- 229910004337 Ti-Ni Inorganic materials 0.000 claims abstract description 9
- 229910011209 Ti—Ni Inorganic materials 0.000 claims abstract description 9
- 239000011888 foil Substances 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 131
- 239000001257 hydrogen Substances 0.000 claims description 121
- 229910052739 hydrogen Inorganic materials 0.000 claims description 121
- 238000005371 permeation separation Methods 0.000 claims description 60
- 239000010409 thin film Substances 0.000 claims description 50
- 239000000758 substrate Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 8
- 238000010791 quenching Methods 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 4
- 229910020012 Nb—Ti Inorganic materials 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 abstract description 6
- 238000007670 refining Methods 0.000 abstract description 3
- 238000005266 casting Methods 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000012298 atmosphere Substances 0.000 description 8
- 125000004429 atom Chemical group 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 101001012040 Pseudomonas aeruginosa (strain ATCC 15692 / DSM 22644 / CIP 104116 / JCM 14847 / LMG 12228 / 1C / PRS 101 / PAO1) Immunomodulating metalloprotease Proteins 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000005496 tempering Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 230000005496 eutectics Effects 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000003949 liquefied natural gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- WIRUZQNBHNAMAB-UHFFFAOYSA-N benzene;cyclohexane Chemical compound C1CCCCC1.C1=CC=CC=C1 WIRUZQNBHNAMAB-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000009760 electrical discharge machining Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
- C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0069—Inorganic membrane manufacture by deposition from the liquid phase, e.g. electrochemical deposition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0074—Inorganic membrane manufacture from melts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0083—Thermal after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/022—Metals
- B01D71/0223—Group 8, 9 or 10 metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
- H01M8/0687—Reactant purification by the use of membranes or filters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/04—Characteristic thickness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0405—Purification by membrane separation
- C01B2203/041—In-situ membrane purification during hydrogen production
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S55/00—Gas separation
- Y10S55/05—Methods of making filter
Definitions
- the present invention is composed of a Ni—Ti—Nb alloy or Nb—Ti—Ni alloy having high mechanical strength, and thus enables a thin film having a thickness of 0.07 mm (70 m) or less.
- the present invention relates to a hydrogen permeation separation thin film that can significantly improve the hydrogen permeation separation performance of the thin film when used for fruits. Background art
- high-purity hydrogen gas has attracted attention as a fuel gas for energy systems such as hydrogen fuel cells and hydrogen gas turbines, and this high-purity hydrogen gas is a mixed gas obtained by electrolyzing water. Reinforced from a hydrogen-containing source gas such as a mixed gas obtained by steam reforming liquefied natural gas (LNG) with a frame made of Ni, for example, as shown in the schematic explanatory diagram of Fig. 5.
- a hydrogen-containing source gas such as a mixed gas obtained by steam reforming liquefied natural gas (LNG) with a frame made of Ni, for example, as shown in the schematic explanatory diagram of Fig. 5.
- Thickness 0.1 ⁇ 3mm hydrogen permeation separation membrane divided into left and right side chambers, and hydrogen containing raw material gas introduction pipe and exhaust gas extraction pipe in left side chamber
- a high-purity hydrogen purifier with a high-purity hydrogen gas extraction pipe attached to the right-hand chamber for example, a stainless steel reaction chamber in the center, is used for the reaction chamber. Heated to ° C and hydrogen-containing raw material from the introduction pipe
- the internal pressure of the right side chamber in which the high purity hydrogen gas separated and purified through the hydrogen permeation separation membrane exists is maintained at 0. IMPa, while the internal pressure of the left side chamber in which the hydrogen-containing source gas exists is 0. It is known that it is produced by separating and refining high-purity hydrogen gas through the hydrogen-permeable separation membrane under the condition of 2 to 0.5 MPa.
- the hydrogen permeable separation membrane performs hydrogen selective movement through the hydrogen permeable separation membrane, for example, a hydrogenated Z dehydrogenation process such as a hydrocarbon steam reforming process or a benzene cyclohexane reaction. It is also well known that it is widely used in chemical reaction processes such as processes.
- FIG. 2 and Fig. 4 are micrographs of the scanning electron microscope (magnification: 2500 times (Fig. 2) and As shown by 4000 times (Fig. 4)), the eutectic structure of NbTi phase containing Ni and NiTi phase containing Nb is used as a base, and the primary NbTi phase (white islands in Fig. 4) Alloy structure dispersed and distributed,
- Ni—Ti—Nb alloy having a component composition of ( ⁇ ) and an alloy structure of ( ⁇ ).
- Patent Document 1 Japanese Patent Laid-Open No. 2005-232491
- the inventors of the present invention can improve the performance of the various chemical reaction apparatuses described above, and in particular, can make a thin film of a hydrogen permeable separation membrane as a structural member thereof.
- the hydrogen permeable separation membrane was
- Nb 10-47 atomic%, 1: 20-52 atomic%, with the remainder being specified as a component composition consisting of Ni and inevitable impurities (however, ⁇ : 20-48 atomic%)
- Alloy melt The hot water is made into a forged foil material with a thickness of 0.07 mm or less by the roll quenching method, and this forged foil material is used in an inert gas atmosphere or a vacuum atmosphere for the purpose of preventing oxidation.
- Temperature 300 to 11 When tempering heat treatment was performed at 00 ° C under the condition of heating and holding for a predetermined time, the resulting tempered heat treatment material became Ni- as shown in the structural photograph (magnification: 2500 times) with a scanning electron microscope in Fig. 1.
- Ni-Ti (Nb) intermetallic compound force (shown in black in Fig. 1) containing a part of Ti in the Ti intermetallic compound in a state where Nb is substituted into the solid solution (shown in black in Fig. 1)
- Ni and Ni Fine grains of Nb-based solid solution alloy formed by solid solution of Ti (shown in white in Fig. 1) have a distributed distribution of alloy structure.
- the Ni-Ti-Nb alloy of this alloy structure is Therefore, it has extremely high mechanical strength. Therefore, in practical use as a hydrogen permeable separation membrane, the film thickness should be 0.07 mm or less. As a result, research results have been obtained that hydrogen permeation separation performance will be improved over a long period of time.
- the alloy melt is made into a forged foil material with a thickness of 0.07 mm or less by the roll quenching method, and the forged foil material is heated in an inert gas atmosphere or in a vacuum atmosphere for the purpose of preventing oxidation.
- the tempered heat treatment material obtained as a result is as shown in the structural photograph (magnification: 4000 times) by scanning electron microscope in Fig.
- Nb is part of Ti in the Ni-Ti intermetallic compound on the substrate (shown in white in Fig. 3) that is made of Nb-based solid solution alloy, which is a solid solution of Ni and Ti in Nb.
- the Ni i-Ti (Nb) intermetallic compound fine particles (shown in black in Fig. 3) contained in a solid solution in the replacement state have a distributed alloy structure.
- the Nb-Ti-Ni alloy with this alloy structure has excellent hydrogen permeation separation performance due to the Nb-based solid solution alloy of the base, and the Ni-Ti (Nb) intermetallic compound of the fine grain is the base.
- Ni-Ti-Nb alloy strength Thickness obtained by roll quenching 0.07mm or less, made of tempered heat-treated heat-treated foil material, having the following component composition (a) and alloy structure (b) A hydrogen permeation separation thin film (hereinafter sometimes referred to as “hydrogen permeation separation thin film (I) J”),
- Nb 10 to 47 atom%
- Ti 20 to 52 atom%
- Ni 20 to 48 atom%
- Ni and Ti are dissolved in Nb in a substrate made of Ni-Ti (Nb) intermetallic compound containing Ni as a solid solution in a state where part of Ti in the Ni-Ti intermetallic compound is substituted by Nb.
- Nb Ni-Ti
- the present invention also provides:
- Nb alloy structure in which fine particles of intermetallic compound are dispersed and distributed
- the hydrogen permeation separation thin film (I) of the present invention can be thinned to a thickness of 0.07 mm or less by the Ni—Ti (Nb) intermetallic compound of the base material having high mechanical strength. Thin Combined with the improvement of hydrogen permeation separation performance due to crystallization and the fact that the Nb-based solid solution alloy that is uniformly dispersed and distributed as fine particles on the substrate exhibits excellent hydrogen permeation separation performance, this is combined with various chemicals. When used in a reactor, it will exhibit excellent hydrogen permeation separation performance over a long period of time.
- the hydrogen permeation separation thin film ( ⁇ ) of the present invention has a fine distribution of Ni—Ti (Nb) intermetallic compound dispersed on a substrate having excellent hydrogen permeation separation performance and Nb-based solid solution alloy strength.
- Nb Ni—Ti
- the thin film can be thinned to a thickness of 0.07 mm or less. This thinning improves the hydrogen permeation separation performance, and the Nb-based solid solution alloy substrate is tangled. Combined with the hydrogen permeation separation performance, the hydrogen permeation separation performance is further improved over a long period of time.
- FIG. 1 is a structural photograph (magnification: 2500 times) of a Ni—Ti—Nb alloy constituting the hydrogen permeable thin film (I) -19 of the present invention by a scanning electron microscope.
- FIG. 2 A structural photograph (magnification: 2500 times) of a Ni-Ti Nb alloy composing the conventional hydrogen permeable membrane (I) 8 by a scanning electron microscope.
- FIG. 3 is a structural photograph (magnification: 4000 times) of the Nb—Ti Ni alloy constituting the hydrogen permeable thin film ( ⁇ ) -6 of the present invention by a scanning electron microscope.
- FIG. 4 A structural photograph (magnification: 4000 times) of a Ni-Ti Nb alloy composing the conventional hydrogen permeable membrane (IV) -8 by a scanning electron microscope.
- FIG. 5 is a schematic explanatory view illustrating a high purity hydrogen purifier.
- the Nb component contains a part of Ti in the Ni-Ti intermetallic compound as described above to form a Ni-Ti (Nb) intermetallic compound constituting the substrate, and In addition to improving hydrogen permeation separation performance, it forms an Nb-based solid solution alloy containing Ni and Ti as a solid solution, and is dispersed and distributed as fine particles in the substrate, thereby exhibiting excellent hydrogen permeation separation performance.
- a certain force If the content is less than 10 atomic%, the thickness of the thin film is less than 0.07 mm. However, if the content exceeds 47 atomic%, the above-described alloy structure cannot be stably secured, even if the thickness is reduced to a thin film. The content was determined to be 10 to 47 atomic%.
- Ni-Ti (Nb) intermetallic compound that forms the substrate is formed in the Ti and Ni components to improve the mechanical strength of the thin film, and thus can be put to practical use with a thickness of 0.07 mm or less.
- Nb Nb-based solid solution alloy that is dispersed and distributed as fine particles in the substrate, and has the effect of increasing the mechanical strength of this.
- the Nb component forms a substrate made of an Nb-based solid solution alloy containing Ni and Ti as a solid solution, and has an effect of exhibiting excellent hydrogen permeation separation performance.
- it contains a part of Ti in the intermetallic compound in a substituted form, it forms fine particles of Ni-Ti (Nb) intermetallic compound and has the effect of improving the hydrogen permeation separation performance of the fine particles.
- the content is less than 48% atom, it becomes difficult to stably obtain the above alloy structure, and the film characteristics vary.
- the content exceeds 70 atomic%, the Ni — The distribution ratio of Ti (Nb) intermetallic compound fine particles is drastically reduced. As a result, the mechanical strength of the thin film is lowered, and it can be put to practical use in a state where the film thickness is reduced to 0.07 mm or less. Therefore, the content was determined to be 48 to 70 atomic%.
- Ni-Ti (Nb) intermetallic compound fine grains dispersed and distributed in the substrate are formed to improve the mechanical strength of the thin film, so that a thin film having a thickness of 0.07 mm or less is realized.
- Nb-based solid solution alloy that constitutes the substrate.
- Content force of either Ti or Ni Ti 15 atomic% or less
- Ni is less than 10% atom
- the desired mechanical strength cannot be ensured for the thin film.
- each Sprayed onto the surface of the roll with 0.05MPa spray pressure, each has a planar dimension of length: 20m x width: 20mm, but the thickness is the average thickness shown in Table 1 (average value at 5 arbitrary locations) ) with Ni- Ti-Nb forms a ⁇ foil material alloy, then was charged with this vacuum furnace, following 10 _2 Pa In the air, each 300 ⁇ : L Hold for 5 hours at a specified temperature within the range of 100 ° C. After tempering heat treatment under furnace cooling conditions, width: 20mm x length: 60mm
- the hydrogen permeation separation thin film of the present invention (hereinafter referred to as the present hydrogen permeation thin film) (I) 1 to (1) 24 was produced by cutting.
- the resulting hydrogen permeable thin films (I) 1 to (1) 24 of the present invention and the conventional hydrogen permeable membranes (I) -1 to (I) -10 have the composition of the energy dispersive fluorescent X-rays When measured using an analyzer, the analysis values were substantially the same as the composition shown in Tables 1 and 2, and the structure was observed using a scanning electron microscope and an X-ray diffractometer.
- the hydrogen permeable thin film (I) -1 to (1) -24 of the present invention as shown in FIG. 1 showing the alloy structure of the hydrogen permeable thin film (I) -19 of the present invention, both are Ni-Ti intermetallic compounds.
- Nb-based solid solution alloy with Ni and Ti dissolved in Nb is dispersed in a Ni-Ti (Nb) intermetallic compound force with solid solution containing Nb as a part of Ti.
- the conventional hydrogen permeable membranes (1) -1 to (1) -10 show the alloy structure of the conventional hydrogen permeable membrane (I) -8 in FIG. Both the eutectic structure of the NiTi phase solid solution of NbTi phase and Nb solid-solved the Ni and the matrix, the primary crystal NbT Xiang showed alloy structure, dispersed distributed in this matrix.
- the thickness of each of the hydrogen permeable thin films (I) 1 to (1) 24 of the present invention and the conventional hydrogen permeable membranes (I) — 1 to (1) — 10 is sputtered by sputtering: 0 1 ⁇ m (Pd II is vapor-deposited (in this case, it may be formed by electroplating method), and horizontal outer dimension: 20mm X vertical outer dimension: 60mm X frame width: 5mm X frame thickness: 0.5mm 5 with the same structure as the hydrogen high-purity refiner having the structure shown in FIG.
- the pressure of the hydrogen permeable membrane (I) 3 to (1) 9 is increased to 0.5 MPa, and that of the conventional hydrogen permeable membrane (I) 1-10 is increased to 0.3 MPa, and maintained for 1 hour under these conditions.
- Measure the flow rate of the permeated hydrogen gas shown as the initial permeated hydrogen flow rate in Tables 1 and 2) with a gas flow meter.
- the hydrogen permeable thin films of the present invention (I) 1 to (1) 24 all have high mechanical strength ensured by the base Ni-Ti (Nb) intermetallic compound, 0.07mm or less is possible, so the Nb-based solid solution alloy dispersed and distributed as fine particles in the substrate exhibits excellent hydrogen permeation separation performance.
- the conventional hydrogen permeable membranes (I) —1 to (1) —10 have the mechanical strength, while the hydrogen permeation separation performance is demonstrated over a long period of time and excellent durability (service life). It is clear that the surface strength of the film cannot be reduced to 0.1 mm or less, which results in low hydrogen permeation separation performance.
- each has a planar dimension of length: 20m X width: 20mm, but the thicknesses are the average thicknesses shown in Table 3 (average values at 5 arbitrary locations) ) to form a ⁇ foil member of Nb-Ti-Ni alloy having, then it was charged with this vacuum furnace, following 10 _2 Pa Air, respectively 300 to: L within a predetermined range of 100 ° C
- the hydrogen permeation separation thin film of the present invention (hereinafter referred to as the present invention hydrogen) is obtained by holding the temperature for 5 hours and then subjecting it to a tempering heat treatment under furnace cooling conditions, and then cutting it into a planar dimension of width: 20 mm x length: 60 mm. (Referred to as a transmissive thin film) (II) 1 to (II) 13 were produced.
- the resulting hydrogen permeable thin films (II) 1 to (II) 13 of the present invention and the conventional hydrogen permeable membranes ( ⁇ ) —1 to ( ⁇ ) —10 are composed of energy dispersive fluorescent X-rays. When measured using an analytical instrument, all showed substantially the same analytical values as the composition shown in Table 3, and the structure was observed using a scanning electron microscope and an X-ray diffractometer. In the hydrogen permeable thin films ( ⁇ ) -1 to ( ⁇ ) -13 of the present invention, as shown in FIG. 3, the alloy structure of the hydrogen permeable thin film (II) -6 of the present invention is shown.
- the conventional hydrogen permeable membrane ( ⁇ ) — 1 to ( ⁇ ) —10 shows the alloy structure of the conventional hydrogen permeable membrane ( ⁇ ) -8. As shown, both the eutectic structure of the NiTi phase solid solution NbT Xiang and Nb solid-solved the Ni and the matrix, the primary crystal NbTi phase showed alloy structure, dispersed distributed in this matrix.
- the hydrogen permeable thin films ( ⁇ ) —1 to ( ⁇ ) —13 of the present invention are all Ni—Ti (Nb) intermetallic compounds in which high mechanical strength is dispersed in the substrate.
- the hydrogen permeation separation performance is further improved and the Nb-based solid solution alloy of the base is excellent.
- the conventional hydrogen permeation membranes ( ⁇ ) —1 to ( ⁇ ) —10 are all mechanical, while exhibiting excellent hydrogen permeation separation performance over a long period of time. It is clear that the surface strength of the film cannot be less than 0.1 mm, and therefore the hydrogen permeation separation performance is low.
- the hydrogen permeation separation thin film of the present invention is made of Ni-Ti-Nb alloy or Nb-Ti-Ni alloy having high mechanical strength, and can be thinned to a thickness of 0.07 mm or less. In practical use, it will exhibit excellent hydrogen permeation separation performance over a long period of time. Therefore, it is necessary to improve the performance of various chemical reactors that use hydrogen permeation separation membranes as structural members. It can respond to satisfaction. Therefore, this invention is very useful industrially.
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- Organic Chemistry (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/281,663 US8105424B2 (en) | 2006-03-08 | 2007-03-08 | Hydrogen permeation/separation thin membrane |
CN2007800078803A CN101394918B (zh) | 2006-03-08 | 2007-03-08 | 氢透过分离薄膜 |
EP07738042A EP1992401B1 (en) | 2006-03-08 | 2007-03-08 | Hydrogen-permeable separation thin membranes |
AU2007225886A AU2007225886B2 (en) | 2006-03-08 | 2007-03-08 | Hydrogen-permeable separation thin membranes |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006-062922 | 2006-03-08 | ||
JP2006062923A JP4953279B2 (ja) | 2006-03-08 | 2006-03-08 | すぐれた水素透過分離性能を発揮する水素透過分離薄膜 |
JP2006-062923 | 2006-03-08 | ||
JP2006062922A JP4953278B2 (ja) | 2006-03-08 | 2006-03-08 | すぐれた水素透過分離性能を発揮する水素透過分離薄膜 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2007105594A1 true WO2007105594A1 (ja) | 2007-09-20 |
Family
ID=38509420
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2007/054552 WO2007105594A1 (ja) | 2006-03-08 | 2007-03-08 | 水素透過分離薄膜 |
Country Status (4)
Country | Link |
---|---|
US (1) | US8105424B2 (ja) |
EP (1) | EP1992401B1 (ja) |
AU (1) | AU2007225886B2 (ja) |
WO (1) | WO2007105594A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101543717A (zh) * | 2008-03-24 | 2009-09-30 | 株式会社日本制钢所 | 氢可渗透模块及其使用方法 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101391500B1 (ko) * | 2010-05-31 | 2014-05-07 | 히타치 긴조쿠 가부시키가이샤 | 수소 분리 합금 및 그 제조 방법 |
US9073007B2 (en) | 2012-02-15 | 2015-07-07 | Samsung Electronics Co., Ltd. | Separation membrane, hydrogen separation membrane including the separation membrane, and hydrogen purifier including the hydrogen separation membrane |
US8900345B2 (en) | 2012-03-19 | 2014-12-02 | Samsung Electronics Co., Ltd. | Separation membrane, hydrogen separation membrane including the separation membrane, and device including the hydrogen separation membrane |
CN109876667A (zh) * | 2019-04-04 | 2019-06-14 | 江苏海发新材料科技有限公司 | 一种多孔不锈钢膜的制备方法 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005232491A (ja) | 2004-02-17 | 2005-09-02 | Ulvac Japan Ltd | 水素分離・精製用複相合金及びその作製方法、並びに水素分離・精製用金属膜及びその作製方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55130801A (en) * | 1979-02-15 | 1980-10-11 | Hill Eugene Farrell | Separation of hydrogen which use coating titaniummzirconium alloy |
WO2004073844A1 (ja) * | 2003-02-24 | 2004-09-02 | Fukuda Metal Foil & Powder Co., Ltd. | 水素分離膜及びその製造方法 |
-
2007
- 2007-03-08 US US12/281,663 patent/US8105424B2/en not_active Expired - Fee Related
- 2007-03-08 EP EP07738042A patent/EP1992401B1/en not_active Expired - Fee Related
- 2007-03-08 WO PCT/JP2007/054552 patent/WO2007105594A1/ja active Application Filing
- 2007-03-08 AU AU2007225886A patent/AU2007225886B2/en not_active Ceased
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005232491A (ja) | 2004-02-17 | 2005-09-02 | Ulvac Japan Ltd | 水素分離・精製用複相合金及びその作製方法、並びに水素分離・精製用金属膜及びその作製方法 |
Non-Patent Citations (2)
Title |
---|
HASHI K. ET AL.: "Ni-Ti-Nb Gokin no Suiso Toka Tokusei", THE JAPAN INSTITUTE OF METALS KOEN GAIYO, vol. 132, 2003, pages 345, XP003017818 * |
See also references of EP1992401A4 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101543717A (zh) * | 2008-03-24 | 2009-09-30 | 株式会社日本制钢所 | 氢可渗透模块及其使用方法 |
EP2106838A1 (en) * | 2008-03-24 | 2009-10-07 | The Japan Steel Works, Ltd. | Hydrogen permeable module and usage thereof |
US8075670B2 (en) | 2008-03-24 | 2011-12-13 | The Japan Steel Works, Ltd. | Hydrogen permeable module and usage thereof |
CN101543717B (zh) * | 2008-03-24 | 2013-10-23 | 株式会社日本制钢所 | 氢可渗透模块及其使用方法 |
Also Published As
Publication number | Publication date |
---|---|
EP1992401B1 (en) | 2012-05-02 |
US20090056549A1 (en) | 2009-03-05 |
AU2007225886A1 (en) | 2007-09-20 |
EP1992401A4 (en) | 2009-06-24 |
US8105424B2 (en) | 2012-01-31 |
AU2007225886B2 (en) | 2010-04-22 |
EP1992401A1 (en) | 2008-11-19 |
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