CN113209838A - High-temperature metal type composite membrane for hydrogen separation and preparation method thereof - Google Patents
High-temperature metal type composite membrane for hydrogen separation and preparation method thereof Download PDFInfo
- Publication number
- CN113209838A CN113209838A CN202110684035.1A CN202110684035A CN113209838A CN 113209838 A CN113209838 A CN 113209838A CN 202110684035 A CN202110684035 A CN 202110684035A CN 113209838 A CN113209838 A CN 113209838A
- Authority
- CN
- China
- Prior art keywords
- alloy
- substrate
- composite membrane
- hydrogen separation
- type composite
- 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
- 239000001257 hydrogen Substances 0.000 title claims abstract description 63
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 63
- 239000012528 membrane Substances 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 238000000926 separation method Methods 0.000 title claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 21
- 239000002184 metal Substances 0.000 title claims abstract description 21
- 125000004435 hydrogen atom Chemical class [H]* 0.000 title abstract 4
- 238000002360 preparation method Methods 0.000 title description 6
- 239000000758 substrate Substances 0.000 claims abstract description 51
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 238000009792 diffusion process Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 16
- 238000004544 sputter deposition Methods 0.000 claims description 15
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 229910045601 alloy Inorganic materials 0.000 claims description 10
- 239000000956 alloy Substances 0.000 claims description 10
- 229910000838 Al alloy Inorganic materials 0.000 claims description 9
- 229910001080 W alloy Inorganic materials 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910000531 Co alloy Inorganic materials 0.000 claims description 6
- 229910004337 Ti-Ni Inorganic materials 0.000 claims description 6
- 229910011209 Ti—Ni Inorganic materials 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000007747 plating Methods 0.000 claims description 6
- 238000010884 ion-beam technique Methods 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 229910052715 tantalum 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
- 229910000599 Cr alloy Inorganic materials 0.000 claims description 3
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 3
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 3
- 238000000231 atomic layer deposition Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 238000010494 dissociation reaction Methods 0.000 claims description 3
- 230000005593 dissociations Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000005566 electron beam evaporation Methods 0.000 claims description 3
- 238000001659 ion-beam spectroscopy Methods 0.000 claims description 3
- 238000001451 molecular beam epitaxy Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 15
- 230000035699 permeability Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000013077 target material Substances 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229910001252 Pd alloy Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin 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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- 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
- C01B3/505—Membranes containing palladium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the technical field of hydrogen separation, in particular to a high-temperature metal type composite membrane for hydrogen separation, which comprises a substrate and a catalyst layer for dissociating hydrogen, wherein the catalyst layer is arranged on the side surface of the substrate, a molybdenum nitride layer for preventing mutual diffusion between the catalyst layer and the substrate under the high-temperature condition is arranged between the substrate and the catalyst layer, and the high-temperature metal type composite membrane is prepared according to the method comprising the step four.
Description
Technical Field
The invention relates to the technical field of hydrogen separation, in particular to a high-temperature metal type composite membrane for hydrogen separation and a preparation method thereof.
Background
Hydrogen has attracted extensive attention as a zero-emission fuel, a carrier of clean energy. However, the hydrogen produced in industry usually contains more harmful impurity gases, and cannot be directly applied. Hydrogen separation membranes are key components in the production of high purity hydrogen.
Among the hydrogen separation membranes, palladium membranes and palladium alloy membranes exhibit good hydrogen catalytic performance, however, palladium metal reserves are small and expensive, further limiting the commercial application of the alloy membranes. Prime for the search for non-noble metal materials capable of replacing Pd alloys. To solve the above problems, two methods for reducing the use of noble metals are mainly adopted at present: 1. a thin layer of hydrogen dissociation catalyst is plated on both sides of the dense hydrogen permeable matrix. 2. Preparing a hydrogen dissociation catalyst layer on the surface of the porous substrate. Among them, the 5B group metals (V, Nb and Ta) have higher hydrogen permeability, lower cost and more abundant resources than Pd, and can be used as compact hydrogen-permeable base. The porous matrix is usually porous stainless steel which is simple to prepare and low in cost. However, the high use temperature (not less than 450 ℃) can cause intermetallic diffusion between the catalyst layer and the substrate to generate a barrier layer with extremely low hydrogen permeation capability, which gradually reduces the hydrogen permeability of the composite membrane and severely limits the use temperature range of the composite membrane, for example, the use temperature of the natural gas reforming hydrogen production in the current main industrial hydrogen production needs to be more than 500 ℃. The molybdenum nitride has abundant resources, has excellent hydrogen catalytic performance in the hydrogen production by water electrolysis, is used as metal ceramic, has excellent high-temperature stability, and is a potential material used as a high-temperature diffusion barrier layer of a hydrogen-permeable alloy composite membrane. Therefore, it is highly desirable to develop a metal composite membrane material including a diffusion barrier layer for use in the field of high temperature hydrogen separation.
In view of this, the invention is particularly proposed.
Disclosure of Invention
Aiming at the defects, the invention provides a high-temperature metal type composite membrane for hydrogen separation, which comprises a substrate and a catalyst layer for dissociating hydrogen, wherein the catalyst layer is arranged on the side surface of the substrate, and a molybdenum nitride layer for preventing the mutual diffusion between the catalyst layer and the substrate under the high-temperature condition is arranged between the substrate and the catalyst layer.
Preferably, the molybdenum nitride layer has a molybdenum and nitrogen atomic percentage of 1:1 to 4: 1.
Preferably, the molybdenum nitride layer has a molybdenum to nitrogen atomic percentage of 2: 1.
Preferably, the substrate is made of a dense material or a porous material.
Preferably, when the substrate is a dense material, the dense material is one of V, Nb, Ta, Mo, Ni, Ti, Pd, Pt, 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 and a Nb-Mo-W alloy;
when the substrate is a porous material, the porous material is porous stainless steel or porous titanium-aluminum alloy.
Preferably, the thickness of the substrate is 20 to 2000 μm, and the substrate is in a sheet shape or a tube shape.
Preferably, the thickness of the catalytic layer is 10-1000 nm.
Preferably, the thickness of the molybdenum nitride layer is 5 to 500 nm.
Preferably, the thickness of the molybdenum nitride layer is 100-200 nm.
The preparation method of the high-temperature metal type composite membrane for hydrogen separation comprises the following steps:
the method comprises the following steps: pretreating a substrate;
step two: cleaning the surface of the substrate by using ion beams;
step three: forming molybdenum nitride layers on two sides of the substrate by adopting one of magnetron sputtering, ion beam sputtering, electron beam evaporation, pulse deposition, molecular beam epitaxy and atomic layer deposition;
step four: and respectively forming catalytic layers on the outer sides of the molybdenum nitride layers by adopting magnetron sputtering or chemical plating.
Preferably, in the step one, the substrate is ultrasonically cleaned for 5-15min by sequentially adopting acetone and absolute ethyl alcohol, the ultrasonic cleaning is repeated for 2-3 times, and then the substrate is washed for 1-2min by using deionized water and then dried.
Preferably, in the third step, magnetron sputtering is adopted to form molybdenum nitride layers on two sides of the substrate respectively; in the fourth step, magnetron sputtering is used to form a catalytic layer on the outer side of the molybdenum nitride layer.
Preferably, the magnetron sputtering conditions in step three include: the vacuum degree in the sputtering cavity is less than 10-4Pa, the temperature of the substrate is 25-600 ℃, the negative bias of the substrate is 0-500V, the total flow of the introduced argon and nitrogen is 20-30sccm, the partial pressure ratio of the argon to the nitrogen is 0.5:0.5-0.95:0.05, the working pressure is 0.5-4Pa, and the sputtering time is 5-120 min;
the magnetron sputtering conditions in the fourth step comprise: the vacuum degree in the sputtering cavity is less than 10-4Pa, the temperature of the substrate is 25-600 ℃, the negative bias of the substrate is 0-500V, the flow of introduced argon is 20-30sccm, the working pressure is 0.5-4Pa, the sputtering power is 50-300W, and the sputtering time is 5-120 min.
An application of high-temperature metal composite membrane for hydrogen separation in hydrogen separation and/or hydrogen purification.
Compared with the prior art, the invention has at least the following advantages:
1. the high-temperature metal type composite membrane provided by the invention reduces the use of noble metal Pd and alloy thereof, and reduces the cost of the composite membrane;
2. the composite membrane of the invention has good stability in high temperature environment, and solves the problems of mutual diffusion and narrow operation temperature range of the composite membrane in high temperature environment;
3. the composite membrane has good high-temperature durability, the service life of the composite membrane is prolonged, and the composite membrane has wide application prospect in the field of high-purity hydrogen production.
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 composite membrane of the present invention;
FIG. 2 is a single-side cross-sectional SEM image of a composite membrane of the present invention;
FIG. 3 is a surface XRD pattern of a composite film according to the present invention;
FIG. 4 is a graph of hydrogen permeation flow for a composite membrane;
description of reference numerals:
1: a substrate; 2: a molybdenum nitride layer; 3: and a catalytic layer.
Detailed Description
The following is a detailed description of several preferred embodiments of the invention, but the invention is not limited to these embodiments only. The invention is intended to cover alternatives, modifications, equivalents, and alternatives that may be included within the spirit and scope of the invention. In the following description of the preferred embodiments of the present invention, specific details are set forth in order to provide a thorough understanding of the present invention, and it will be apparent to those skilled in the art that the present invention may be practiced without these specific details.
Example one
As shown in figure 1, the high-temperature metal type composite membrane for hydrogen separation comprises a substrate 1 and a catalytic layer 3 for dissociating hydrogen, wherein the catalytic layer 3 is arranged on the side surface of the substrate 1, and the substrate 1 is Nb56Ti23Ni21And a molybdenum nitride layer 2 which is arranged between the substrate 1 and the catalyst layer 3 and prevents the catalyst layer 3 and the substrate 1 from mutual diffusion under high temperature.
In the present embodiment, the molybdenum and nitrogen atomic percentages in the molybdenum nitride layer 2 are 1:1 to 4: 1.
In the present embodiment, the atomic percentage of molybdenum and nitrogen in the molybdenum nitride layer 2 is 2: 1.
In the present embodiment, the substrate 1 is made of a dense material or a porous material
In this embodiment, when the substrate is a dense material, the dense material is one of V, Nb, Ta, Mo, Ni, Ti, Pd, Pt, 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, and a Nb-Mo-W alloy;
when the substrate is a porous material, the porous material is porous stainless steel or porous titanium-aluminum alloy.
In the present embodiment, the thickness of the substrate 1 is 20 to 2000 μm, and the substrate 1 is in a sheet shape or a tube shape.
In this embodiment, the thickness of the catalytic layer 3 is 10 to 1000 nm.
In the present embodiment, the thickness of the molybdenum nitride layer 2 is 5 to 500 nm.
In the present embodiment, the thickness of the molybdenum nitride layer 2 is 100-200 nm.
When the performance test is carried out on the produced and formed composite membrane on equipment, the hydrogen transmission rate of the composite membrane is more than or equal to 1 multiplied by 10- 3mol m-2s-1Specifically (4-6). times.10-3mol m-2s-1The operation temperature of the composite membrane is 300-550 ℃, in particular 450-550 ℃, and in addition, the hydrogen permeation flow of the composite membrane is more than or equal to 1 multiplied by 10-8mol H2 m-1s-1Pa-0.5Specifically (2-5). times.10-8molH2 m-1s-1Pa-0.5。
Example two
A preparation method of a high-temperature metal type composite membrane for hydrogen separation comprises the following steps:
the method comprises the following steps: pretreating a substrate; adopts analytically pure acetone and absolute ethyl alcohol to Nb56Ti23Ni21Ultrasonically cleaning the wafer for 10min, repeating for 2-3 times, washing with deionized water for 1min, and drying in a drying oven at 120 deg.C.
Step two: cleaning the surface of the substrate by using ion beams; pretreated Nb56Ti23Ni21The wafer, the molybdenum target and the palladium target are respectively arranged on a sample table and a target head of a magnetron sputtering coating chamber, and the vacuum degree of the chamber is pumped to 10 by using a molecular pump-4Setting electron beam current below Pa, argon flow rate of 5sccm, chamber pressure of 0.5Pa, and applying argon ion beam to Nb56Ti23Ni21And cleaning the surface of the wafer for 30 min.
Step three: by magnetron sputteringForming a molybdenum nitride layer on two sides of the substrate by one of ion beam sputtering, electron beam evaporation, pulse deposition, molecular beam epitaxy and atomic layer deposition; mixing Nb with56Ti23Ni21Heating the wafer to room temperature, setting the bias voltage to be 0, the sputtering power to be 50W, the chamber pressure to be 0.5Pa, pre-sputtering the molybdenum target material for 5min, after cleaning the pollutants on the surface of the target material, increasing the sputtering power to 200W, setting the bias voltage to be 150V, the sputtering power to be 200W, the partial pressure ratio of argon to nitrogen to be 0.9:0.1, and the time to be 5min, and carrying out Nb-removing treatment on the wafer56Ti23Ni21And plating a molybdenum nitride layer on the surface of the wafer.
Step four: changing the sputtering target material into a palladium target material and plating Nb with a molybdenum nitride layer56Ti23Ni21Heating the wafer to 300 ℃, sputtering power of 200W, chamber pressure of 0.5Pa and time of 15min, and plating the Nb with the molybdenum nitride layer on the surface56Ti23Ni21The wafer is plated with a Pd catalyst layer.
The SEM image of the material cross section is shown in FIG. 2, and the surface characterization XRD is shown in FIG. 3. The results in FIG. 2 show that: the magnetron sputtering molybdenum nitride layer has good compactness and uniform thickness; the results in FIG. 3 show that: and preparing the molybdenum nitride with the molybdenum nitride layer of 2:1 by magnetron sputtering.
The hydrogen permeation performance obtained by performing the hydrogen permeation experiment using the hydrogen permeation device as shown in fig. 4 is related to time. The results in FIG. 4 show that: the hydrogen permeability of the composite membrane of the embodiment is superior to that of Pd under long time, the decrease of the hydrogen permeability is small along with the increase of the time, and the hydrogen permeability phi under 773K is 3.8 multiplied by 10-8molH2m-1s-1Pa-0.5Has high temperature stability and hydrogen permeability.
EXAMPLE III
Referring to the preparation method of example two, the steps and parameters were the same as those of example two except that the time for plating the molybdenum nitride layer in step three was changed to 20 min.
The SEM image of the cross section of the composite membrane of the embodiment is shown in FIG. 2; as can be seen from FIG. 2, the magnetron sputtering molybdenum nitride layer has good compactness and uniform thickness, and the thickness is about 200 nm.
Composition of the embodimentThe hydrogen permeation performance of the membrane as a function of time is shown in FIG. 4; the results in FIG. 4 show that: the hydrogen permeability phi of the composite membrane of this example was 1.0X 10 under 773K long time experiments-8molH2m-1s-1Pa-0.5The composite film is lower than the molybdenum nitride layer because the thickness is thicker, which is not beneficial to hydrogen diffusion, but the hydrogen permeability does not decline with the increase of time, and the composite film has excellent high-temperature stability.
Compared with the prior art, the invention has the following advantages:
1. the high-temperature metal type composite membrane provided by the invention reduces the use of noble metal Pd and alloy thereof, and reduces the cost of the composite membrane;
2. the composite membrane of the invention has good stability in high temperature environment, and solves the problems of mutual diffusion and narrow operation temperature range of the composite membrane in high temperature environment;
3. the composite membrane has good high-temperature durability, the service life of the composite membrane is prolonged, and the composite membrane has wide application prospect in the field of high-purity hydrogen production.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (10)
1. A high-temperature metal type composite membrane for hydrogen separation is characterized in that: the hydrogen dissociation catalyst comprises a base body (1) and a catalyst layer (3) for dissociating hydrogen, wherein the catalyst layer (3) is arranged on the side surface of the base body (1), and a molybdenum nitride layer (2) for preventing mutual diffusion between the catalyst layer (3) and the base body (1) under the high-temperature condition is arranged between the base body (1) and the catalyst layer (3).
2. A high temperature metal type composite membrane for hydrogen separation according to claim 1, wherein the molybdenum and nitrogen atomic percentage in the molybdenum nitride layer (2) is 1: 1-4: 1.
3. A high temperature metal type composite membrane for hydrogen separation according to claim 2, wherein the molybdenum and nitrogen atomic percentage in the molybdenum nitride layer (2) is 2: 1.
4. A high temperature metallic composite membrane for hydrogen separation according to claim 1, wherein the substrate (1) is made of a dense material or a porous material;
when the substrate is a compact material, the compact material is one of V, Nb, Ta, Mo, Ni, Ti, Pd, Pt, V-Ni alloy, V-Cr alloy, V-Cu alloy, V-Fe alloy, V-Al alloy, V-Co alloy, V-Mo alloy, V-W alloy, V-Ti-Ni alloy, V-Fe-Al alloy, V-Mo-W alloy, Nb-Ti-Ni alloy, Nb-Ti-Co alloy and Nb-Mo-W alloy;
when the substrate is a porous material, the porous material is porous stainless steel or porous titanium-aluminum alloy.
5. A high temperature metal type composite membrane for hydrogen separation according to claim 1, wherein the thickness of the base body (1) is 20-2000 μm, and the base body (1) is in a sheet or tube shape; the thickness of the catalytic layer (3) is 10-1000 nm; the thickness of the molybdenum nitride layer (2) is 5-500 nm; the thickness of the molybdenum nitride layer (2) is 100-200 nm.
6. A method for preparing a high temperature metal type composite membrane for hydrogen separation according to any one of claims 1 to 5, characterized by comprising the steps of:
the method comprises the following steps: pretreating a substrate;
step two: cleaning the surface of the substrate by using ion beams;
step three: forming molybdenum nitride layers on two sides of the substrate by adopting one of magnetron sputtering, ion beam sputtering, electron beam evaporation, pulse deposition, molecular beam epitaxy and atomic layer deposition;
step four: and respectively forming catalytic layers on the outer sides of the molybdenum nitride layers by adopting magnetron sputtering or chemical plating.
7. A method for preparing a high temperature metal type composite membrane for hydrogen separation according to claim 6,
in the first step, the substrate is ultrasonically cleaned for 5-15min by sequentially adopting acetone and absolute ethyl alcohol, the ultrasonic cleaning is repeated for 2-3 times, then deionized water is used for washing for 1-2min, and then drying is carried out.
8. The method for preparing a high-temperature metal-type composite membrane for hydrogen separation according to claim 6, wherein in the third step, magnetron sputtering is adopted to form molybdenum nitride layers on two sides of the substrate respectively; in the fourth step, magnetron sputtering is used to form a catalytic layer on the outer side of the molybdenum nitride layer.
9. The method for preparing a high-temperature metal-type composite membrane for hydrogen separation according to claim 8,
the magnetron sputtering conditions in the third step include: the vacuum degree in the sputtering cavity is less than 10-4Pa, the temperature of the substrate is 25-600 ℃, the negative bias of the substrate is 0-500V, the total flow of the introduced argon and nitrogen is 20-30sccm, the partial pressure ratio of the argon to the nitrogen is 0.5:0.5-0.95:0.05, the working pressure is 0.5-4Pa, and the sputtering time is 5-120 min;
the magnetron sputtering conditions in the fourth step comprise: the vacuum degree in the sputtering cavity is less than 10-4Pa, the temperature of the substrate is 25-600 ℃, the negative bias of the substrate is 0-500V, the flow of introduced argon is 20-30sccm, the working pressure is 0.5-4Pa, the sputtering power is 50-300W, and the sputtering time is 5-120 min.
10. Use of a high temperature metal type composite membrane for hydrogen separation according to any one of claims 1 to 9 in hydrogen separation and/or hydrogen purification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110684035.1A CN113209838A (en) | 2021-06-21 | 2021-06-21 | High-temperature metal type composite membrane for hydrogen separation and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110684035.1A CN113209838A (en) | 2021-06-21 | 2021-06-21 | High-temperature metal type composite membrane for hydrogen separation and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113209838A true CN113209838A (en) | 2021-08-06 |
Family
ID=77080696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110684035.1A Pending CN113209838A (en) | 2021-06-21 | 2021-06-21 | High-temperature metal type composite membrane for hydrogen separation and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113209838A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134158A (en) * | 2006-08-31 | 2008-03-05 | 比亚迪股份有限公司 | Compound film for separating hydrogen gas and method for preparing the same and the hydrogen gas segregator |
| CN106057928A (en) * | 2016-07-27 | 2016-10-26 | 华南理工大学 | Stainless steel flexible substrate copper-indium-gallium-selenium thin-film solar cell capable of blocking spread of iron effectively and preparation method thereof |
| CN111841339A (en) * | 2020-07-23 | 2020-10-30 | 李新中 | Composite membrane for hydrogen separation and preparation method and application thereof |
| CN112062606A (en) * | 2020-07-23 | 2020-12-11 | 李新中 | Hydrogen separation and purification membrane and preparation method and application thereof |
| CN112957912A (en) * | 2021-01-29 | 2021-06-15 | 中国工程物理研究院材料研究所 | Multilayer selective hydrogen permeation composite membrane and preparation and application thereof |
| CN215996231U (en) * | 2021-06-21 | 2022-03-11 | 曾祥燕 | High-temperature metal type composite membrane for hydrogen separation |
-
2021
- 2021-06-21 CN CN202110684035.1A patent/CN113209838A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134158A (en) * | 2006-08-31 | 2008-03-05 | 比亚迪股份有限公司 | Compound film for separating hydrogen gas and method for preparing the same and the hydrogen gas segregator |
| CN106057928A (en) * | 2016-07-27 | 2016-10-26 | 华南理工大学 | Stainless steel flexible substrate copper-indium-gallium-selenium thin-film solar cell capable of blocking spread of iron effectively and preparation method thereof |
| CN111841339A (en) * | 2020-07-23 | 2020-10-30 | 李新中 | Composite membrane for hydrogen separation and preparation method and application thereof |
| CN112062606A (en) * | 2020-07-23 | 2020-12-11 | 李新中 | Hydrogen separation and purification membrane and preparation method and application thereof |
| CN112957912A (en) * | 2021-01-29 | 2021-06-15 | 中国工程物理研究院材料研究所 | Multilayer selective hydrogen permeation composite membrane and preparation and application thereof |
| CN215996231U (en) * | 2021-06-21 | 2022-03-11 | 曾祥燕 | High-temperature metal type composite membrane for hydrogen separation |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Nam et al. | Preparation of a palladium alloy composite membrane supported in a porous stainless steel by vacuum electrodeposition | |
| CN112609165B (en) | Composite coating on surface of bipolar plate of stainless steel-based fuel cell and preparation method thereof | |
| JP5199332B2 (en) | Method for producing palladium alloy composite membrane for hydrogen gas separation | |
| US4544473A (en) | Catalytic electrolytic electrode | |
| WO2021259046A1 (en) | Method for preparing cr-al-c based max phase coating and use thereof | |
| CN105047958B (en) | Graphene composite coating for fuel battery metal pole plate and preparation method thereof | |
| CN113235062A (en) | MAX-phase multilayer composite coating and preparation method and application thereof | |
| CN112957912B (en) | Multilayer selective hydrogen permeation composite membrane and preparation and application thereof | |
| JP2015227506A (en) | Method of preparing alloys of platinum-group metals and early transition metals | |
| JP2018006300A (en) | Metal separator for fuel cell and fuel cell using the same | |
| CN115000444B (en) | Multilayer composite carbon coating, preparation method and application thereof, fuel cell bipolar plate and fuel cell | |
| JPH11286785A (en) | Hydrogen-permeable membrane and its preparation | |
| CN111841339A (en) | Composite membrane for hydrogen separation and preparation method and application thereof | |
| US20130092025A1 (en) | Defectless hydrogen separation membrane, production method for defectless hydrogen separation membrane and hydrogen separation method | |
| CN110880608A (en) | Metal bipolar plate composite film layer for hydrogen fuel cell and preparation method thereof | |
| JPS63171617A (en) | Composite membrane excellent in permselectivity of hydrogen and its production | |
| CN114481048A (en) | High-conductivity corrosion-resistant amorphous/nanocrystalline composite coexistent coating and preparation method and application thereof | |
| CN113209838A (en) | High-temperature metal type composite membrane for hydrogen separation and preparation method thereof | |
| CN212396398U (en) | Composite membrane for hydrogen separation | |
| CN112176285A (en) | Novel niobium carbide film for hydrogen separation and preparation method thereof | |
| JP3645088B2 (en) | Hydrogen permeable membrane and method for producing the same | |
| CN215996231U (en) | High-temperature metal type composite membrane for hydrogen separation | |
| JP2001170460A (en) | Hydrogen separating material and producing method therefor | |
| CN116837405A (en) | High-conductivity corrosion-resistant gas diffusion layer and preparation method thereof | |
| Xue et al. | Amorphous Ni–B alloy/ceramic composite membrane prepared by an improved electroless plating technique |
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 | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220708 Address after: 130 Flourishing Street, Nangang District, Harbin City, Heilongjiang Province Applicant after: Li Xinzhong Address before: 341000 No. 42, Baowu group, Baitian village, Shuixi Town, Zhanggong District, Ganzhou City, Jiangxi Province Applicant before: Zeng Xiangyan |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210806 |