CN112062606A - Hydrogen separation and purification membrane and preparation method and application thereof - Google Patents
Hydrogen separation and purification membrane and preparation method and application thereof Download PDFInfo
- Publication number
- CN112062606A CN112062606A CN202010715072.XA CN202010715072A CN112062606A CN 112062606 A CN112062606 A CN 112062606A CN 202010715072 A CN202010715072 A CN 202010715072A CN 112062606 A CN112062606 A CN 112062606A
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- layer
- alloy
- molybdenum carbide
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 214
- 239000001257 hydrogen Substances 0.000 title claims abstract description 214
- 239000012528 membrane Substances 0.000 title claims abstract description 90
- 238000000926 separation method Methods 0.000 title claims abstract description 84
- 238000000746 purification Methods 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 125000004435 hydrogen atom Chemical class [H]* 0.000 title 1
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 108
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 106
- 239000000758 substrate Substances 0.000 claims abstract description 90
- 229910039444 MoC Inorganic materials 0.000 claims abstract description 64
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000010408 film Substances 0.000 claims abstract description 35
- 230000006798 recombination Effects 0.000 claims abstract description 25
- 238000005215 recombination Methods 0.000 claims abstract description 25
- 238000009792 diffusion process Methods 0.000 claims abstract description 17
- 239000010409 thin film Substances 0.000 claims abstract description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 65
- 229910052786 argon Inorganic materials 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 19
- 238000004140 cleaning Methods 0.000 claims description 18
- 238000001659 ion-beam spectroscopy Methods 0.000 claims description 18
- 238000010884 ion-beam technique Methods 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 16
- 238000004544 sputter deposition Methods 0.000 claims description 14
- 239000013077 target material Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 12
- 238000007747 plating Methods 0.000 claims description 12
- 229910001080 W alloy Inorganic materials 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 7
- 229910000838 Al alloy Inorganic materials 0.000 claims description 6
- 229910000531 Co alloy Inorganic materials 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 5
- 238000011010 flushing procedure Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910004337 Ti-Ni Inorganic materials 0.000 claims description 4
- 229910011209 Ti—Ni Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910000599 Cr alloy Inorganic materials 0.000 claims description 3
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 3
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 3
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052755 nonmetal Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 238000000231 atomic layer deposition Methods 0.000 claims description 2
- 238000005566 electron beam evaporation Methods 0.000 claims description 2
- 238000001451 molecular beam epitaxy Methods 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000011049 filling Methods 0.000 claims 1
- 230000035699 permeability Effects 0.000 abstract description 13
- 239000002131 composite material Substances 0.000 description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- 238000010494 dissociation reaction Methods 0.000 description 12
- 230000005593 dissociations Effects 0.000 description 12
- 238000011144 upstream manufacturing Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 238000001341 grazing-angle X-ray diffraction Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 230000004907 flux Effects 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000011888 foil Substances 0.000 description 7
- 238000011160 research Methods 0.000 description 6
- 229910003178 Mo2C Inorganic materials 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- -1 argon ions Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000008429 bread Nutrition 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- IMFJNXMOPRISHP-UHFFFAOYSA-N [Mo].[Nb].[W] Chemical compound [Mo].[Nb].[W] IMFJNXMOPRISHP-UHFFFAOYSA-N 0.000 description 1
- UEGQDNWDKJWZFK-UHFFFAOYSA-N [Ti].[Nb].[Co] Chemical compound [Ti].[Nb].[Co] UEGQDNWDKJWZFK-UHFFFAOYSA-N 0.000 description 1
- KHOFBPOVUAPBTF-UHFFFAOYSA-N [Ti].[Ni].[Nb] Chemical compound [Ti].[Ni].[Nb] KHOFBPOVUAPBTF-UHFFFAOYSA-N 0.000 description 1
- BUUNILCKFRLOQJ-UHFFFAOYSA-N [Ti].[V].[Ni] Chemical compound [Ti].[V].[Ni] BUUNILCKFRLOQJ-UHFFFAOYSA-N 0.000 description 1
- WFISYBKOIKMYLZ-UHFFFAOYSA-N [V].[Cr] Chemical compound [V].[Cr] WFISYBKOIKMYLZ-UHFFFAOYSA-N 0.000 description 1
- KPZUWETZTXCDED-UHFFFAOYSA-N [V].[Cu] Chemical compound [V].[Cu] KPZUWETZTXCDED-UHFFFAOYSA-N 0.000 description 1
- GXTVJIIYRCYTNM-UHFFFAOYSA-N [V].[Mo].[W] Chemical compound [V].[Mo].[W] GXTVJIIYRCYTNM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PTXMVOUNAHFTFC-UHFFFAOYSA-N alumane;vanadium Chemical compound [AlH3].[V] PTXMVOUNAHFTFC-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- LLESOAREQXNYOK-UHFFFAOYSA-N cobalt vanadium Chemical compound [V].[Co] LLESOAREQXNYOK-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005324 grain boundary diffusion Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000033001 locomotion Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- WUJISAYEUPRJOG-UHFFFAOYSA-N molybdenum vanadium Chemical compound [V].[Mo] WUJISAYEUPRJOG-UHFFFAOYSA-N 0.000 description 1
- QXYJCZRRLLQGCR-UHFFFAOYSA-N molybdenum(IV) oxide Inorganic materials O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 1
- HBVFXTAPOLSOPB-UHFFFAOYSA-N nickel vanadium Chemical group [V].[Ni] HBVFXTAPOLSOPB-UHFFFAOYSA-N 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- NWJUARNXABNMDW-UHFFFAOYSA-N tungsten vanadium Chemical compound [W]=[V] NWJUARNXABNMDW-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/87—Ceramics
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
- C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
- C04B41/5057—Carbides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0635—Carbides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/28—Vacuum evaporation by wave energy or particle radiation
- C23C14/30—Vacuum evaporation by wave energy or particle radiation by electron bombardment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/46—Sputtering by ion beam produced by an external ion source
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/32—Carbides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
-
- 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
Abstract
The invention provides a hydrogen separation and purification membrane and a preparation method and application thereof. The hydrogen separation and purification membrane comprises a hydrogen separation layer, a hydrogen diffusion layer and a hydrogen recombination layer which are sequentially stacked from top to bottom, wherein the hydrogen diffusion layer is a substrate layer, and the hydrogen separation layer and the hydrogen recombination layer are molybdenum carbide thin films; in particular, the molybdenum carbide in the molybdenum carbide film is in a crystalline structure. The hydrogen separation and purification membrane of the invention improves the hydrogen permeability during hydrogen separation and purification, reduces the use cost, and provides a new choice for realizing novel, cheap, efficient and stable hydrogen separation and purification.
Description
Technical Field
The invention relates to the technical field of hydrogen separation, in particular to a hydrogen separation and purification membrane and a preparation method and application thereof.
Background
Currently, energy problems and environmental problems become major factors restricting industrial development, and hydrogen energy has many advantages such as large reserves, high calorific value, and the like, so that the hydrogen energy has attracted attention in the field of new energy. Since the purity of hydrogen used in many fields such as semiconductors, hydrogen energy automobiles, aerospace and the like is at least 99.999%, an efficient, cheap and recyclable method for obtaining high-purity hydrogen is urgently needed.
At present, high-purity hydrogen is mainly obtained by a pressure swing adsorption or low-temperature distillation method, and a membrane separation method is the most effective hydrogen purification technology at present, wherein a hydrogen-filtering palladium membrane is widely applied in the field of hydrogen separation and purification. However, palladium metal is a precious metal element, is scarce in resources and expensive, and is prone to hydrogen embrittlement at low temperature, so the research on the metal-based hydrogen permeable membrane is focused on the research on the composite membrane and the search for the surface catalytic membrane having the same Pd-like catalytic dissociation property.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a hydrogen separation and purification membrane, a preparation method and application thereof, wherein the hydrogen separation and purification membrane improves the hydrogen permeability during hydrogen separation and purification and reduces the use cost.
The invention provides a hydrogen separation and purification membrane which comprises a hydrogen separation layer, a hydrogen diffusion layer and a hydrogen recombination layer which are sequentially stacked from top to bottom, wherein the hydrogen diffusion layer is a substrate layer, and the hydrogen separation layer and the hydrogen recombination layer are molybdenum carbide thin films.
The research finds that the molybdenum carbide film has certain catalytic capacity combined with hydrogen, has hydrogen dissociation catalytic capacity similar to that of Pd, is more grafted into Pt group elements than some transition group metal elements and noble metals, and has good hydrogen combination energy and exchange current density which show that the molybdenum carbide film is a potential catalyst capable of replacing Pd. The hydrogen separation and purification membrane is plated with the molybdenum carbide thin films on two sides of the substrate layer, so that the hydrogen separation/recombination performance is provided, and the use cost is greatly reduced.
Preferably, the molybdenum carbide in the molybdenum carbide film is in a crystalline structure; that is, the molybdenum carbide thin film is a crystalline molybdenum carbide thin film. The research finds that: the molybdenum carbide film with the crystalline structure can improve the transmission rate of hydrogen in a nanometer grain boundary, so that the hydrogen permeation performance is greatly improved.
The ion beam sputtering technique is under a higher vacuum (10)-2Pa), high energy argon plasma pair Mo excited from ion source2Bombarding the C target material to excite a large amount of high-energy Mo and C sputtering particles, and enabling the particles to move to reach the V substrate at a high speed and deposit on the V substrate to form Mo2C/V composite membrane. In the ion beam sputtering process, the high-energy argon plasma excited from the ion source bombards the target at a certain incidence angle, the flight tracks of the incident argon ions and the sputtered target atoms do not intersect, atom clusters generated by cascade collision are not easy to occur, and the formation of the regularly arranged atomic-level high-quality film is facilitated. Secondly, the target material is bombarded by the ion beam from a long distance, the two are relatively independent, an argon plasma area involved in the magnetron sputtering process is not existed, non-ionized gas molecules are not existed, the vacuum degree required by the working pressure is higher, and the vacuum degree is two orders of magnitude higher than that of the magnetron sputtering, so that the defects of thin film oxidation and the like caused by gas inclusion can be avoided.
The plating method of the molybdenum carbide film with the crystalline structure is not strictly limited. In one embodiment, a crystalline-structured molybdenum carbide thin film can be obtained by controlling the substrate temperature to 400 ℃ or higher during ion beam sputtering; more specifically, the substrate temperature can be controlled to be 400-600 ℃; in this case, the substrate negative bias is not strictly limited, and may be, for example, 0 to 500V.
In another embodiment, a molybdenum carbide thin film with a crystalline structure can also be obtained by controlling the negative bias of the substrate to be more than 300V during ion beam sputtering; more specifically, the substrate negative bias voltage can be controlled to be 300-500V; in this case, the substrate temperature is not strictly limited, and may be, for example, 20 to 600 ℃.
The molar ratio of Mo to C in the molybdenum carbide film is not critical, and may be, for example, (1-5): 1-3)Further (1-4) to (2-3); in one embodiment, the molar ratio of Mo to C in the molybdenum carbide film is 2: 1, in which case Mo may be selected2C is taken as a material.
The thicknesses of the hydrogen dissociation layer, the hydrogen diffusion layer and the hydrogen recombination layer are not strictly limited; specifically, the thickness of the hydrogen dissociation layer may be 5 to 500nm, preferably 10 to 300nm, more preferably 50 to 150nm, and still more preferably 100 nm; the thickness of the hydrogen diffusion layer may be 20 to 20000 μm, preferably 50 to 15000 μm, more preferably 50 to 150 μm, and still more preferably 100 μm; the thickness of the hydrogen recombination layer may be 5 to 500nm, preferably 10 to 300nm, more preferably 50 to 150nm, and still more preferably 100 nm.
In the present invention, the base layer may be a metal layer, a metal alloy layer or a non-metallic ceramic layer; wherein the metal in the metal layer is V, Nb, Ta, Mo, Ni, Ti, Pd, Pt or porous stainless steel; the metal alloy in the metal alloy layer is a V-Ni alloy, a V-Cr alloy, a V-Cu alloy, a V-Fe alloy, a V-Al alloy, a V-Co alloy, a V-Mo alloy, a V-W alloy, a V-Ti-Ni alloy, a V-Fe-Al alloy, a V-Mo-W alloy, a Nb-Ti-Ni alloy, a Nb-Ti-Co alloy, a Nb-Mo-W alloy or a high-entropy hydrogen-permeating alloy; the non-metal ceramic layer is a porous alumina ceramic layer, a porous zirconia ceramic layer or a zeolite layer. Particularly, the adoption of the porous ceramic materials such as the porous alumina, the porous zirconia, the zeolite and the like can better improve the purification effect of the hydrogen separation and purification materials under wide temperature range and different industrial conditions.
That is, the metal layer is a vanadium metal layer, a niobium metal layer, a tantalum metal layer, a molybdenum metal layer, a nickel metal layer, a titanium metal layer, a palladium metal layer, a platinum metal layer or a porous stainless steel metal layer; the metal alloy layer is a vanadium-nickel alloy layer, a vanadium-chromium alloy layer, a vanadium-copper alloy layer, a vanadium-iron alloy layer, a vanadium-aluminum alloy layer, a vanadium-cobalt alloy layer, a vanadium-molybdenum alloy layer, a vanadium-tungsten alloy layer, a vanadium-titanium-nickel alloy layer, a vanadium-iron-aluminum alloy layer, a vanadium-molybdenum-tungsten alloy layer, a niobium-titanium-nickel alloy layer, a niobium-titanium-cobalt alloy layer, a niobium-molybdenum-tungsten alloy layer or a high-entropy hydrogen-permeating alloy.
The hydrogen permeation flow of the hydrogen separation and purification membrane is more than or equal to 6 multiplied by 10 at the temperature of 600 DEG C-8mol H2 m-1 s-1Pa-0.5Preferably ≥ 9.5X 10-8mol H2 m-1s-1Pa-0.5And has excellent hydrogen permeability.
The invention also provides a preparation method of the hydrogen separation and purification membrane, which comprises the following steps: and plating molybdenum carbide films on two sides of the substrate layer respectively.
The invention does not strictly limit the way of plating the molybdenum carbide film; specifically, the method for applying the molybdenum carbide film may be ion beam sputtering, magnetron sputtering, electron beam evaporation, pulse deposition, molecular beam epitaxy or atomic layer deposition.
In one embodiment, the substrate layer may be coated with molybdenum carbide thin films on both sides thereof by an ion beam sputtering method; the molybdenum carbide film obtained by the method has fine and uniform particles, high quality, firm combination with the substrate, capability of performing sputtering coating on targets of almost any material and better coverage on the steps of the substrate material with larger surface roughness.
Further, the substrate temperature may be controlled to 400 ℃ or higher, and more preferably to 400-600 ℃ during ion beam sputtering.
The research finds that: ion beam sputtering is different from magnetron sputtering, the energy of ion beam flow is extremely high, the energy of particles bombarded by the ion beam flow is also very high, when high-energy particles are deposited on a substrate with a lower temperature, the cooling speed is too high, atoms cannot be rearranged in time, and are frozen in a short-range ordered and long-range disordered state, and finally amorphous molybdenum carbide is formed. Since the hydrogen permeation process of molybdenum carbide belongs to grain boundary diffusion, and the grain boundary in an amorphous state is less unfavorable for hydrogen transmission, the crystallization treatment of amorphous molybdenum carbide is necessary. The invention discovers that the substrate is preheated in the deposition process of the film, so that the sputtered atoms are further diffused by the thermal motion energy after reaching the substrate base plate, which is equivalent to annealing the film, and the crystallization of molybdenum carbide is facilitated due to small supercooling degree; in particular, a crystalline molybdenum carbide film with complete crystallization can be formed at a substrate temperature of 400 ℃ or higher, has excellent hydrogen catalytic dissociation or recombination performance, and can further improve Mo2C/V complexHydrogen permeability of the composite membrane.
Further, during ion beam sputtering, the substrate negative bias can be controlled to be equal to or more than 300V, and more preferably 300-500V.
The research finds that: in the ion beam sputtering process, positive particles and electrons are generated due to bombardment of an argon ion beam, and under the action of negative bias, the positive particles are accelerated to cause that the average kinetic energy is increased when the positive particles reach the vicinity of a substrate surface, the thermal action with the substrate surface is intensified, so that nucleation and growth can be realized at relatively low substrate temperature, and finally a film with good crystallinity is formed, wherein the action is similar to the thermal effect caused by high deposition temperature; in particular, a crystalline molybdenum carbide thin film in which a substrate negative bias of 300V or more can form a crystalline molybdenum carbide thin film completely crystallized, which has excellent hydrogen catalytic dissociation or recombination properties and can further improve Mo2Hydrogen permeability of the C/V composite membrane.
In addition, the amorphous sample can be heated to the annealing temperature at a higher speed, the temperature is kept in a protective atmosphere for a certain time to ensure that the amorphous sample is completely crystallized, and the nanocrystalline can be obtained after the amorphous sample is cooled to the room temperature; wherein, the variation range of the annealing temperature can be 600-1200 ℃.
More specifically, the method for preparing a hydrogen separation purification membrane of the present invention comprises:
s1: closing a baffle plate in front of the sputtered substrate material, flushing argon gas into an ion source, generating low-energy argon plasma beams to bombard the molybdenum carbide target material on the target table, and cleaning the surface of the molybdenum carbide target material;
s2: and opening a baffle plate before the sputtered substrate material, flushing argon gas into an ion source, generating a high-energy argon plasma beam to bombard the molybdenum carbide target on the target table, and depositing the sputtered particles generated on the molybdenum carbide target on the substrate layer to form a molybdenum carbide film.
Further, before step S1, the method further includes: carrying out ultrasonic cleaning on the substrate material; specifically, the ultrasonic cleaning may include: sequentially ultrasonically cleaning with acetone, anhydrous alcohol and deionized water for 5-15min, and oven drying.
In step S1 of the present invention, argon or the like is usedThe conditions for cleaning the molybdenum carbide target material by the ion beam comprise: the vacuum degree in the sputtering cavity is less than 10-4Pa; the temperature of the substrate is 25-600 ℃; the negative bias voltage of the substrate is 0-300V; introducing argon gas flow of 3-10 sccm; the working pressure is 0.2-0.8 Pa; ion energy of the low-energy ion beam is 800-1400 eV; the beam current density is 8-12mA/cm2(ii) a The continuous bombardment time is 5-10 min.
In step S2 of the present invention, the conditions for sputtering the molybdenum carbide target with the argon plasma beam include: the vacuum degree in the sputtering cavity is less than 10-4Pa; the substrate temperature is 25-600 ℃, preferably 200-600 ℃, and more preferably 400-600 ℃; the substrate negative bias is 0-500V, preferably 300-500V; introducing argon gas flow of 3-10 sccm; the working pressure is 0.2-0.8 Pa; the ion energy of the high-energy ion beam is 1500-; the beam current density is 12-18mA/cm2(ii) a The continuous bombardment time is 5-60 min.
The invention also provides the application of the hydrogen separation and purification membrane or the hydrogen separation and purification membrane prepared by the preparation method in hydrogen separation and/or hydrogen purification.
Compared with the prior art, the molybdenum carbide film is used as the surface hydrogen dissociation layer and the hydrogen recombination layer, so that the noble metal Pd is thoroughly replaced, and the application cost is greatly reduced; particularly, the invention also realizes the improvement of hydrogen permeability by a grain boundary regulation and control technical means, and Mo subjected to grain boundary regulation and control2The hydrogen permeation flow rate of the C/V hydrogen permeation composite membrane at 600 ℃ is 9.5 multiplied by 10-8mol H2 m-1s-1Pa-0.5Compared with the performance without regulation and control, the performance is improved by more than 10 times. The invention greatly improves the hydrogen permeability during hydrogen separation and purification, reduces the use cost, and provides a new choice for materials and devices for realizing novel, cheap, efficient and stable hydrogen separation and purification.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic structural view of a hydrogen separation purification membrane of the present invention;
FIG. 2 is a schematic view of the operation principle of the hydrogen separation and purification membrane of the present invention;
FIG. 3 shows Mo prepared in examples 1-4 at different substrate temperatures without negative bias of the substrate2GIXRD pattern of C/V hydrogen separation purification membrane material;
FIG. 4 shows Mo prepared at different substrate temperatures loaded with different substrate negative biases for examples 5-82GIXRD pattern of C/V hydrogen separation purification membrane material;
FIG. 5 shows Mo prepared in example 22The change curve of the hydrogen flux of the C/V hydrogen separation and purification composite membrane material along with the upstream pressure under the negative bias of an unloaded substrate;
FIG. 6 shows Mo prepared in example 62The change curve of hydrogen flux of the C/V hydrogen separation and purification membrane material along with the upstream pressure under the negative bias of a substrate loaded with 300V;
FIG. 7 shows Mo compounds prepared in examples 2 to 42The results of comparing the hydrogen permeation performance of the C/V hydrogen separation and purification membrane material with that of the Pd and V materials;
FIG. 8 shows Mo compounds prepared in examples 4 and 92The results of the comparison test of the hydrogen permeation performance of the C/V hydrogen separation and purification membrane are obtained;
FIG. 9 shows Mo prepared in example 42XPS spectra of Mo 3d in C;
FIG. 10 shows Mo prepared in example 92XPS spectra of Mo 3d in C;
FIG. 11 shows Mo compounds prepared in examples 2 to 42And (3) a durable hydrogen permeation test curve of the C/V hydrogen separation and purification membrane.
Description of reference numerals:
1: a hydrogen release layer; 2: a hydrogen diffusion layer; 3: a hydrogen recombination layer.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms also include the plural forms unless the context clearly dictates otherwise, and further, it is understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, devices, components, and/or combinations thereof.
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
As shown in fig. 1, the hydrogen separation purification membrane of the present embodiment is composed of a hydrogen separation layer 1, a hydrogen diffusion layer 2, and a hydrogen recombination layer 3, which are sequentially stacked from top to bottom; wherein the hydrogen dissociation layer 1 is Mo with a thickness of 100nm2C hydrogen dissociation layer, hydrogen diffusion layer 2 is metal V foil with thickness of 100 μm, and hydrogen recombination layer 3 is Mo with thickness of 100nm2C hydrogen recombination layer.
The operation principle of the hydrogen separation and purification membrane is shown in fig. 2. The hydrogen gas can permeate through the hydrogen separation layer 1, the hydrogen diffusion layer 2 and the hydrogen recombination layer 3 of the hydrogen separation purification membrane, and other impurities cannot permeate through the hydrogen separation purification membrane, so that the hydrogen gas can be separated and purified.
The specific preparation steps of the hydrogen separation purification membrane of the present example are as follows:
1. cleaning a substrate
And cleaning the sheared metal V foil substrate by using an ultrasonic cleaner, wherein during cleaning, acetone, absolute ethyl alcohol and deionized water are sequentially adopted to respectively perform ultrasonic cleaning for 10min, and then drying treatment is performed.
2. Cleaning target material
Cleaning the molybdenum carbide target material by using argon ion beams, wherein during cleaning, a baffle plate in front of a sputtered substrate material is closed firstly, and the vacuum degree in a sputtering cavity is controlled to be less than 1 multiplied by 10-4Pa, argon gas flow of 8sccm, working pressure of 0.5Pa, ion energy of low-energy ion beam of 1400eV, and beam density of 10mA/cm2The duration of continuous bombardment was 8 min.
3. Preparation of the Hydrogen Release layer
And opening a baffle plate before the sputtered substrate material, flushing argon gas into an ion source, generating high-energy argon plasma beams to bombard the molybdenum carbide target on the target table, and depositing sputtered particles generated on the molybdenum carbide target on the substrate to form a molybdenum carbide film (namely a hydrogen dissociation layer 1).
When the argon ion beam is used for sputtering the molybdenum carbide target material, the vacuum degree in the sputtering cavity is less than 1 multiplied by 10-4Pa, substrate temperature of 25 deg.C, substrate negative bias of 0V, argon flow of 8sccm, working pressure of 0.5Pa, ion energy of high-energy ion beam of 2000eV, and beam density of 15mA/cm2The duration of bombardment was 30 min.
4. Preparation of Hydrogen recombination layer
Turning over the sample without opening the furnace, and plating the other side of the V foil substrate again by the same method and parameters as the step 4 to form a molybdenum carbide film (namely the hydrogen recombination layer 3); and after the furnace body is naturally cooled, taking out the sample to obtain the hydrogen separation and purification membrane, and sealing and storing.
The GIXRD pattern of the hydrogen separation purification membrane prepared in this example is shown in fig. 3. From FIG. 3, it can be seen that Mo is contained in the membrane for separating and purifying hydrogen of the present embodiment2C is a 'steamed bread peak', belongs to an amorphous state, and can also see a diffraction peak of the substrate V foil due to the fact that the thick bottom of the C is very thin.
Example 2
Referring to the preparation method of example 1, the steps and parameters were the same as those of example 1 except that the substrate temperature was controlled to 200 ℃ and the substrate negative bias voltage was controlled to 0V at the time of plating in steps 3 and 4.
The GIXRD pattern of the hydrogen separation purification membrane prepared in this example is shown in fig. 3. From FIG. 3, it can be seen that the hydrogen separation purification of the present exampleMo in film2C is a "steamed bread peak" and is enhanced and still amorphous.
Different pressures are given to the two ends of the hydrogen separation and purification membrane of the embodiment by using the hydrogen permeation device, and the obtained change curve of the hydrogen flux along with the upstream pressure is shown in fig. 5; in FIG. 5, the ordinate represents the hydrogen permeation flow rate in mol H in terms of the number of moles of hydrogen permeated per unit area of the membrane per unit time at different temperatures2 m-2s-1In which P isuThe upper end pressure of the composite membrane is shown, n is the Hivitter index, the hydrogen permeation process at low temperature is close to 0.5, the whole hydrogen permeation process is mainly limited by bulk diffusion, the hydrogen permeation process at high temperature is close to 1.0, and the whole hydrogen permeation process is mainly limited by the surface.
The relationship between the hydrogen permeability and the temperature of the hydrogen separation and purification membrane of this example is shown in fig. 7, in which the ordinate in fig. 7 represents the hydrogen permeability coefficient (the molar quantity of hydrogen passing through the membrane sheet per unit thickness per unit time under the unit upstream and downstream pressure difference) and the unit is mol H2 m-2s-1Pa-0.5(ii) a The abscissa represents temperature or 1000/temperature, and the upper abscissa in fig. 7 is temperature in degrees c; the abscissa at the bottom in FIG. 7 is 1000/T, T representing the Kelvin temperature in K. As can be seen from FIG. 7, the hydrogen permeation flux of the hydrogen separation purification membrane of this example at 600 ℃ was 5.3X 10-9mol H2 m-1s-1Pa-0.5。
Example 3
Referring to the preparation method of example 1, the steps and parameters were the same as those of example 1 except that the substrate temperature was controlled to 400 ℃ and the substrate negative bias voltage was controlled to 0V in the plating in steps 3 and 4.
The GIXRD pattern of the hydrogen separation purification membrane of this example is shown in fig. 3; from FIG. 3, it can be seen that Mo is contained in the membrane for separating and purifying hydrogen of the present embodiment2C is a crystalline film, because Mo is promoted by the increase of the substrate temperature during film coating2The diffusion speed of atoms in the deposition process of C is not frozen, thereby forming crystalline Mo2C。
Hydrogen separation purification of the present exampleThe hydrogen permeability of the membrane is plotted against temperature in figure 7; as can be seen from FIG. 7, the hydrogen permeation flux of the hydrogen separation purification membrane of this example at 600 ℃ was 6.4X 10-8mol H2 m-1s-1Pa-0.5。
Example 4
Referring to the preparation method of example 1, the steps and parameters were the same as those of example 1 except that the substrate temperature was controlled to 600 ℃ and the substrate negative bias voltage was controlled to 0V in the plating in steps 3 and 4.
The GIXRD pattern of the hydrogen separation purification membrane of this example is shown in fig. 3; it can be seen from FIG. 3 that Mo in the membrane for separating and purifying hydrogen of this example is2C remained crystalline, thus indicating that Mo increases with substrate temperature2C gradually evolves from amorphous to crystalline.
The relationship between the hydrogen permeability and the temperature of the hydrogen separation purification membrane of the present example is shown in fig. 7; the results of FIG. 7 show that the hydrogen permeation performance of the hydrogen separation and purification membrane of the present example is better than that of Pd at the hydrogen permeation temperature of 530 ℃ or higher, and particularly the hydrogen permeation flow rate at 600 ℃ is 9.5X 10-8mol H2 m-1 s-1Pa-0.5Compared with the performance which is not regulated and controlled, the performance is improved by more than 10 times, and the high-temperature hydrogen permeability is excellent.
Example 5
The hydrogen separation and purification membrane of the embodiment consists of a hydrogen separation layer, a hydrogen diffusion layer and a hydrogen recombination layer which are sequentially stacked from top to bottom; wherein the hydrogen dissociation layer is 100nm thick Mo2C hydrogen dissociation layer, hydrogen diffusion layer is metal V foil with thickness of 100 μm, and hydrogen recombination layer is Mo with thickness of 100nm2C hydrogen recombination layer.
The specific preparation steps of the hydrogen separation purification membrane of the present example are as follows:
1. cleaning a substrate
And cleaning the sheared metal V foil substrate by using an ultrasonic cleaner, wherein during cleaning, acetone, absolute ethyl alcohol and deionized water are sequentially adopted to respectively perform ultrasonic cleaning for 10min, and then drying treatment is performed.
2. Cleaning target material
Cleaning the molybdenum carbide target material by using argon ion beams, wherein during cleaning, a baffle plate in front of a sputtered substrate material is closed firstly, and the vacuum degree in a sputtering cavity is controlled to be less than 1 multiplied by 10-4Pa, argon gas flow of 8sccm, working pressure of 0.5Pa, ion energy of low-energy ion beam of 1400eV, and beam density of 10mA/cm2The duration of continuous bombardment was 8 min.
3. Preparation of the Hydrogen Release layer
And opening a baffle plate before the sputtered substrate material, flushing argon gas into an ion source, generating a high-energy argon plasma beam to bombard the molybdenum carbide target on the target table, and depositing the sputtered particles generated on the molybdenum carbide target on the substrate to form a molybdenum carbide film.
When the argon ion beam is used for sputtering the molybdenum carbide target material, the vacuum degree in the sputtering cavity is less than 1 multiplied by 10-4Pa, substrate temperature of 25 deg.C, substrate negative bias of 300V, argon flow of 8sccm, working pressure of 0.5Pa, ion energy of high-energy ion beam of 2000eV, and beam density of 15mA/cm2The duration of bombardment was 30 min.
4. Preparation of Hydrogen recombination layer
Turning over the sample without opening the furnace, and plating the other side of the V foil substrate again by the same method and parameters as the step 4 to form a hydrogen recombination layer; and after the furnace body is naturally cooled, taking out the sample to obtain the hydrogen separation and purification membrane, and sealing and storing.
The GIXRD pattern of the hydrogen separation and purification membrane of this example is shown in fig. 4; as can be seen from comparative examples 1 to 4, even if the substrate temperature is at the lowest 25 ℃, Mo is promoted by the negative bias of 300V only2C is crystallized.
Example 6
Referring to the preparation method of example 5, the steps and parameters were the same as those of example 5 except that the substrate temperature was controlled to 200 ℃ and the substrate negative bias voltage was controlled to 300V in the plating in steps 3 and 4.
The GIXRD pattern of the hydrogen separation and purification membrane of this example is shown in fig. 4; comparative examples 1 to 4 it can be seen that Mo can be promoted by the negative bias of 300V only2C is crystallized.
Different pressures are given to the two ends of the hydrogen separation and purification membrane of the embodiment by using the hydrogen permeation device, and the obtained change curve of the hydrogen flux along with the upstream pressure is shown in FIG. 6; as can be seen from comparative example 2, the hydrogen permeation flux of the hydrogen separation purification membrane is greatly increased under the negative bias of 300V load.
Example 7
Referring to the preparation method of example 5, the steps and parameters were the same as those of example 5 except that the substrate temperature was controlled to 400 ℃ and the substrate negative bias voltage was controlled to 300V in the plating in steps 3 and 4.
The GIXRD pattern of the hydrogen separation and purification membrane of this example is shown in fig. 4; comparative examples 1 to 4 it can be seen that Mo can be promoted by the negative bias of 300V only2C is crystallized.
Example 8
Referring to the preparation method of example 5, the steps and parameters were the same as those of example 5 except that the substrate temperature was controlled to 600 ℃ and the substrate negative bias voltage was controlled to 300V in the plating in steps 3 and 4.
The GIXRD pattern of the hydrogen separation purification membrane of this example is shown in fig. 4; comparative examples 1 to 4 it can be seen that Mo can be promoted by the negative bias of 300V only2C is crystallized.
Example 9
Except Mo with the same film thickness prepared by adopting a magnetron sputtering mode2The process was substantially the same as in example 4 except that the C/V hydrogen separation purification membrane was used.
FIG. 8 shows Mo compounds prepared in examples 4 and 92The results of the comparison test of the hydrogen permeation performance of the C/V hydrogen separation and purification membrane are obtained; the results in FIG. 8 show that: mo of example 42The hydrogen permeation coefficient phi of the C/V hydrogen separation and purification membrane at the hydrogen permeation temperature of 450-600 ℃ is all higher than that of the Mo with the same membrane thickness prepared by the magnetron sputtering method in the embodiment 92The performance of the C/V film is greatly improved.
FIGS. 9 and 10 show Mo compounds prepared in examples 4 and 9, respectively2XPS spectra of Mo 3d in C. In the 3d map of Mo, Mo can be divided into two valence states +2 and + 4; wherein, Mo 2+3d attributable to Mo3/2And 3d5/2Corresponding to 228.3eV and231.6eV, which have a slight red shift of their peak compared to the prior art (228.1eV,231.2eV), which may be associated with the formation of traces of MoC; mo4+Non-reactive oxide MoO mainly derived from thin film surface2Corresponding to 230.6eV and 233.8eV, respectively. Mo prepared by ion beam sputtering method in the same manner as in example 42C film comparison, in the film prepared by magnetron sputtering in example 9, MoO2The peak area is greatly increased, and the doping of the inactive MoO is higher2Will influence Mo2C catalytic activity of the thin film, thus illustrating Mo produced by ion beam sputtering2The performance of the C/V hydrogen separation and purification membrane is more excellent.
Test example 1
The hydrogen purification tests were carried out by using the hydrogen separation purification membranes of examples 2 to 4, respectively, and the test methods were as follows:
a hydrogen permeation device and a composite membrane material are utilized to form a set of hydrogen purification device, a hydrogen permeation mold is divided into an upstream portion and a downstream portion, and a composite membrane is placed between the two portions of the mold. In order to make the mould have good air tightness and prevent the diaphragm from being subjected to large stress concentration in the fastening process, oxygen-free copper gaskets with the outer diameter of 16 mm and the inner diameter of 8mm are placed on two sides of the diaphragm, and the air tightness is checked. The composite membrane sample is secured by bolts in the upstream and downstream dies, which are then attached to the equipment at the upstream and downstream ports. After the pipeline is connected, 0.15MPa of hydrogen-containing mixed gas is filled from the upstream end, the temperature is heated to 773K under the condition and is kept for 30min, so that the temperature in the die and each part of the composite membrane is uniform, and the composite membrane is activated at the same time. When the hydrogen absorption of the composite membrane reaches saturation, the pressure reading is stable, and the hydrogen permeability test is started: the upstream pressure was increased from 0.2MPa at intervals of 0.05MPa until it increased to 0.7MPa, and a stable hydrogen permeation flow rate value was recorded for each pressure, and the downstream pressure was maintained at 0.1MPa at all times.
In addition, the stability of the hydrogen permeation flow of the composite membrane is tested by the following method: taking another composite membrane which is not subjected to hydrogen permeation, performing the earlier preparation steps as described above, maintaining the temperature at 773K, the upstream pressure at 0.5MPa and the downstream pressure at 0.1MPa when performing a hydrogen permeation test, performing the hydrogen permeation test for 6 hours, and recording the change of the hydrogen permeation flow along with the time.
FIG. 11 shows Mo prepared at different substrate temperatures during ion beam sputtering at 600 deg.C2The durable hydrogen permeation test curve of the C/V composite membrane is that the upstream pressure is 0.8MPa, and the downstream pressure is 0.1 MPa; the results in FIG. 11 show that: example 3 crystalline Mo prepared at a substrate temperature of 400 deg.C2C/V composite films and crystalline Mo prepared in example 4 at a substrate temperature of 600 deg.C2The C/V composite film has good hydrogen permeation and lasting stability, while the amorphous Mo prepared in the example 2 at the substrate temperature of 200 DEG C2The hydrogen permeation flux of the C/V composite membrane is slowly increased along with the time, which may be related to the slow structure transformation of the amorphous membrane into the crystalline state in the hydrogen permeation process.
In addition, after gas mass spectrometry test, the purity of the finally obtained hydrogen is more than or equal to 99.999 percent.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The hydrogen separation and purification membrane is characterized by comprising a hydrogen separation layer, a hydrogen diffusion layer and a hydrogen recombination layer which are sequentially stacked from top to bottom, wherein the hydrogen diffusion layer is a substrate layer, and the hydrogen separation layer and the hydrogen recombination layer are both molybdenum carbide thin films;
preferably, the molybdenum carbide in the molybdenum carbide film is in a crystalline structure;
preferably, the molybdenum carbide thin film is coated on two sides of the substrate layer in an ion beam sputtering mode;
preferably, the molar ratio of Mo to C in the molybdenum carbide film is (1-5): 1-3, more preferably (1-4): 2-3, and still more preferably 2: 1.
2. the hydrogen separation purification membrane according to claim 1, wherein the thickness of the hydrogen separation layer is 5 to 500nm, preferably 10 to 300nm, more preferably 50 to 150nm, and still more preferably 100 nm; the thickness of the hydrogen diffusion layer is 20 to 20000 μm, preferably 50 to 15000 μm, more preferably 50 to 150 μm, and still more preferably 100 μm; the thickness of the hydrogen recombination layer is 5 to 500nm, preferably 10 to 300nm, more preferably 50 to 150nm, and still more preferably 100 nm.
3. The hydrogen separation purification membrane according to claim 1, wherein the substrate layer is a metal layer, a metal alloy layer or a non-metal ceramic layer;
preferably, the metal in the metal layer is V, Nb, Ta, Mo, Ni, Ti, Pd, Pt or porous stainless steel;
preferably, the metal alloy in the metal alloy layer is a V-Ni alloy, a V-Cr alloy, a V-Cu alloy, a V-Fe alloy, a V-Al alloy, a V-Co alloy, a V-Mo alloy, a V-W alloy, a V-Ti-Ni alloy, a V-Fe-Al alloy, a V-Mo-W alloy, a Nb-Ti-Ni alloy, a Nb-Ti-Co alloy, a Nb-Mo-W alloy or a high-entropy hydrogen-permeating alloy;
preferably, the non-metal ceramic layer is a porous alumina ceramic layer, a porous zirconia ceramic layer or a zeolite layer.
4. The membrane for separating and purifying hydrogen as claimed in claim 1, wherein the hydrogen permeation flow rate of the membrane for separating and purifying hydrogen is not less than 6 x 10 at 600 ℃-8mol H2 m-1 s-1 Pa-0.5Preferably ≥ 9.5X 10-8mol H2 m-1 s-1 Pa-0.5。
5. The method for producing a hydrogen separation purification membrane as claimed in any one of claims 1 to 4, comprising: plating molybdenum carbide films on two sides of the substrate layer respectively;
preferably, the method for applying the molybdenum carbide film is ion beam sputtering, magnetron sputtering, electron beam evaporation, pulse deposition, molecular beam epitaxy or atomic layer deposition.
6. The method according to claim 5, wherein the molybdenum carbide thin films are respectively plated on both sides of the substrate layer by an ion beam sputtering method;
preferably, the substrate temperature is controlled to be more than or equal to 400 ℃ during ion beam sputtering, and more preferably to be 400-600 ℃;
preferably, the substrate negative bias voltage is controlled to be equal to or more than 300V, and more preferably 300-500V during ion beam sputtering.
7. The method of claim 6, comprising:
s1: closing a baffle plate in front of the sputtered substrate material, flushing argon gas into an ion source, generating low-energy argon plasma beams to bombard the molybdenum carbide target material on the target table, and cleaning the surface of the molybdenum carbide target material;
s2: opening a baffle plate before the sputtered substrate material, and filling argon gas into an ion source to generate a high-energy argon plasma beam to bombard a molybdenum carbide target on a target table, wherein sputtered particles generated on the molybdenum carbide target are deposited on a substrate layer to form a molybdenum carbide film;
preferably, before step S1, the method further includes: carrying out ultrasonic cleaning on the substrate material;
preferably, the ultrasonic cleaning comprises: sequentially ultrasonically cleaning with acetone, anhydrous alcohol and deionized water for 5-15min, and oven drying.
8. The method according to claim 7, wherein the conditions for cleaning the molybdenum carbide target using the argon plasma beam in step S1 include: the vacuum degree in the sputtering cavity is less than 10-4Pa; the temperature of the substrate is 25-600 ℃; the negative bias voltage of the substrate is 0-300V; introducing argon gas flow of 3-10 sccm; the working pressure is 0.2-0.8 Pa; ion energy of the low-energy ion beam is 800-1400 eV; the beam current density is 8-12mA/cm2(ii) a The continuous bombardment time is 5-10 min.
9. According to claimThe preparation method of 7, wherein in step S2, the conditions for sputtering the molybdenum carbide target material with the argon plasma beam include: the vacuum degree in the sputtering cavity is less than 10-4Pa; the substrate temperature is 25-600 ℃, preferably 200-600 ℃, and more preferably 400-600 ℃; the substrate negative bias is 0-500V, preferably 300-500V; introducing argon gas flow of 3-10 sccm; the working pressure is 0.2-0.8 Pa; the ion energy of the high-energy ion beam is 1500-; the beam current density is 12-18mA/cm2(ii) a The continuous bombardment time is 5-60 min.
10. Use of the hydrogen separation purification membrane according to claim 1 or the hydrogen separation purification membrane produced by the production method according to any one of claims 5 to 9 for hydrogen separation and/or hydrogen purification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010715072.XA CN112062606A (en) | 2020-07-23 | 2020-07-23 | Hydrogen separation and purification membrane and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010715072.XA CN112062606A (en) | 2020-07-23 | 2020-07-23 | Hydrogen separation and purification membrane and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112062606A true CN112062606A (en) | 2020-12-11 |
Family
ID=73657749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010715072.XA Pending CN112062606A (en) | 2020-07-23 | 2020-07-23 | Hydrogen separation and purification membrane and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112062606A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113209838A (en) * | 2021-06-21 | 2021-08-06 | 曾祥燕 | High-temperature metal type composite membrane for hydrogen separation and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110229379A1 (en) * | 2010-03-22 | 2011-09-22 | Way J Douglas | Stable Catalyst Layers for Hydrogen Permeable Composite Membranes |
| CN104860806A (en) * | 2014-02-21 | 2015-08-26 | 中国科学院大连化学物理研究所 | Applications of molybdenum carbide nanobelts in preparing benzaldehyde via phenylcarbinol dehydrogenation |
| CN106011784A (en) * | 2016-06-03 | 2016-10-12 | 武汉工程大学 | Method for preparing alpha-phase molybdenum carbide crystals through microwave plasma enhanced chemical vapor deposition |
| CN110614105A (en) * | 2019-09-25 | 2019-12-27 | 上海应用技术大学 | Mo for hydrogen evolution2C/NiCoSex heterojunction electrocatalytic material and preparation method thereof |
-
2020
- 2020-07-23 CN CN202010715072.XA patent/CN112062606A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110229379A1 (en) * | 2010-03-22 | 2011-09-22 | Way J Douglas | Stable Catalyst Layers for Hydrogen Permeable Composite Membranes |
| CN104860806A (en) * | 2014-02-21 | 2015-08-26 | 中国科学院大连化学物理研究所 | Applications of molybdenum carbide nanobelts in preparing benzaldehyde via phenylcarbinol dehydrogenation |
| CN106011784A (en) * | 2016-06-03 | 2016-10-12 | 武汉工程大学 | Method for preparing alpha-phase molybdenum carbide crystals through microwave plasma enhanced chemical vapor deposition |
| CN110614105A (en) * | 2019-09-25 | 2019-12-27 | 上海应用技术大学 | Mo for hydrogen evolution2C/NiCoSex heterojunction electrocatalytic material and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113209838A (en) * | 2021-06-21 | 2021-08-06 | 曾祥燕 | High-temperature metal type composite membrane for hydrogen separation and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Vu et al. | Physical vapour deposition of vanadium dioxide for thermochromic smart window applications | |
| Nam et al. | A study on the palladium/nickel composite membrane by vacuum electrodeposition | |
| CN107620033B (en) | Preparation method of high-purity strong dense MAX phase coating | |
| Hoang et al. | Fabrication and characterization of dual sputtered Pd–Cu alloy films for hydrogen separation membranes | |
| CN113235062B (en) | MAX-phase multilayer composite coating and preparation method and application thereof | |
| CN111344807B (en) | Zirconium alloy cladding tube with improved high temperature oxidation resistance and method of making same | |
| CN113413895B (en) | Production equipment and production method of thin film catalyst | |
| Al-Mufachi et al. | Effects of thin film Pd deposition on the hydrogen permeability of Pd60Cu40 wt% alloy membranes | |
| CN105908131B (en) | It is a kind of can thermally grown oxide aluminium film TiAl coatings and preparation method thereof | |
| CN111621752A (en) | Preparation process of AlCrSiN/AlCrN/AlCrON/AlCrN multilayer nano composite coating | |
| CN108149211A (en) | A kind of Mg-TM surpasses MULTILAYER COMPOSITE hydrogen storage film and preparation method thereof | |
| JP2021504567A (en) | Al-Cr based ceramic coating with enhanced thermal stability | |
| JP2018527693A (en) | Method for producing nanostructured layer | |
| WO2023197469A1 (en) | High-conductivity corrosion-resistant amorphous/nanocrystalline composite coexisting coating, and preparation method therefor and use thereof | |
| CN112062606A (en) | Hydrogen separation and purification membrane and preparation method and application thereof | |
| CN111841339A (en) | Composite membrane for hydrogen separation and preparation method and application thereof | |
| CN212403966U (en) | Hydrogen separation purification membrane | |
| CN112176285A (en) | Novel niobium carbide film for hydrogen separation and preparation method thereof | |
| CN111218657B (en) | Amorphous tungsten-based high-entropy alloy thin film material and preparation method thereof | |
| JPH11286785A (en) | Hydrogen-permeable membrane and its preparation | |
| CN108588646B (en) | Method for preparing amorphous/amorphous nano multilayer film with improved plasticity | |
| JP3645088B2 (en) | Hydrogen permeable membrane and method for producing the same | |
| CN212396398U (en) | Composite membrane for hydrogen separation | |
| CN109487209B (en) | High-hardness MAX-phase ceramic coating and preparation method thereof | |
| CN114959569A (en) | Cr (chromium) 2 Preparation method of AlC diffusion impervious layer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Li Xinzhong Inventor after: Yin Xiangxin Inventor after: Li Xinhua Inventor before: Li Xin Inventor before: Yin Xiangxin Inventor before: Li Xinhua |
|
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220129 Address after: 241000 No. 4, Jinye Road, Sanshan Economic Development Zone, Wuhu City, Anhui Province Applicant after: Wuhu China hydrogen New Energy Technology Co.,Ltd. Address before: 150006 No. 130, prosperous street, Nangang District, Harbin, Heilongjiang. Applicant before: Li Xinzhong |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201211 |