CN111217327A - Application of nano magnesium-based hydrogen storage alloy powder - Google Patents
Application of nano magnesium-based hydrogen storage alloy powder Download PDFInfo
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- CN111217327A CN111217327A CN201811418893.6A CN201811418893A CN111217327A CN 111217327 A CN111217327 A CN 111217327A CN 201811418893 A CN201811418893 A CN 201811418893A CN 111217327 A CN111217327 A CN 111217327A
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- hydrogen
- storage alloy
- alloy powder
- hydrogen storage
- nano magnesium
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 153
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 153
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 65
- 239000000956 alloy Substances 0.000 title claims abstract description 65
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 64
- 239000011777 magnesium Substances 0.000 title claims abstract description 64
- 238000003860 storage Methods 0.000 title claims abstract description 64
- 239000000843 powder Substances 0.000 title claims abstract description 56
- 239000007789 gas Substances 0.000 claims abstract description 49
- 239000012629 purifying agent Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 238000012856 packing Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 14
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 150000004678 hydrides Chemical class 0.000 description 18
- 238000000926 separation method Methods 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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- 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
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention relates to an application of nano magnesium-based hydrogen storage alloy powder; in particular to a method for separating or purifying hydrogen by utilizing nano magnesium-based hydrogen storage alloy powder. The invention takes nano magnesium-based hydrogen storage alloy powder as a separating and/or purifying agent to separate and/or purify hydrogen from hydrogen-containing mixed gas. The invention utilizes the magnesium-based hydrogen storage alloy to carry out selective chemical absorption on hydrogen at low temperature and decompose and release hydrogen at slightly high temperature. The method has low requirements on the pressure and the hydrogen content of the mixed gas, the obtained hydrogen has high purity, the energy consumption is low, the process is simple, safe and reliable, and the method is convenient for large-scale industrial application.
Description
Technical Field
The invention relates to an application of nano magnesium-based hydrogen storage alloy powder; in particular to a method for separating or purifying hydrogen by utilizing nano magnesium-based hydrogen storage alloy powder.
Background
Hydrogen is a gas with wide application in the industries of metallurgy, chemical industry, pharmacy, electronics and the like. During the production and use of hydrogen, the hydrogen is often mixed with other gases to obtain a mixed gas containing the hydrogen. Alternatively, in some processes, hydrogen gas is produced as a byproduct, which is separated for economic use. Therefore, the separation of high-purity hydrogen from the mixed gas is a key technology. The existing hydrogen separation technology mainly comprises the following steps: (1) pressure swing adsorption; (2) cryogenic separation; (3) membrane separation, and the like.
In pressure swing adsorption, an adsorbent that is difficult to adsorb hydrogen is used to adsorb other impurity gases in a mixed gas, and the adsorbent is desorbed during pressure reduction or vacuum pumping to regenerate the adsorbent. The cryogenic treatment is to separate hydrogen by condensing the impurity gas in the mixed gas with boiling point higher than that of hydrogen at low temperature. Both of them have the disadvantages of high energy consumption, complex process and low purity of the obtained hydrogen.
The membrane separation is to realize gas separation and purification by adopting the property that a specific membrane material has selective permeation and diffusion to gas. But has the disadvantage of lower permeation flux. The metal palladium membrane can obtain ultrahigh-purity hydrogen and has good stability, but expensive metal palladium is used, and the cost is very high.
The technology of separating and/or purifying hydrogen gas by using nano magnesium-based hydrogen storage alloy powder is rarely reported in the prior literature.
Disclosure of Invention
The research finds that: many metals and alloys can react with hydrogen under certain conditions, have the function of storing and releasing hydrogen, and are used as hydrogen storage materials. Meanwhile, further research finds that the magnesium-based hydrogen storage alloy powder with the nano structure has good selective absorption on hydrogen in hydrogen-containing mixed gas under very low hydrogen partial pressure, and the magnesium-based hydrogen storage alloy can be decomposed to release hydrogen by heating the magnesium-based hydrogen storage alloy to a certain temperature.
Based on the above findings and the shortcomings of the prior art, the present invention provides an application of nano magnesium-based hydrogen storage alloy powder, and particularly provides a method for separating and/or purifying hydrogen from hydrogen-containing mixed gas by using nano-structured magnesium-based hydrogen storage alloy.
The invention relates to application of nano magnesium-based hydrogen storage alloy powder, which takes the nano magnesium-based hydrogen storage alloy powder as a separating and/or purifying agent to separate and/or purify hydrogen from hydrogen-containing mixed gas.
As a preferred scheme, the invention relates to the application of nano magnesium-based hydrogen storage alloy powder; placing the nano magnesium-based hydrogen storage alloy powder in reaction equipment, and introducing hydrogen-containing mixed gas at the temperature of A ℃; then stopping introducing the hydrogen-containing mixed gas, and heating the temperature of the nano magnesium-based hydrogen storage alloy powder to B ℃; collecting hydrogen; a is less than or equal to 300; the value range of B is 200-500, and B is larger than A. Preferably, A is 0 to 200.
The invention relates to application of nano magnesium-based hydrogen storage alloy powder, wherein the grain size of the nano magnesium-based hydrogen storage alloy powder is 1-500 nm.
The invention relates to an application of nano magnesium-based hydrogen storage alloy powder, which is prepared by placing the nano magnesium-based hydrogen storage alloy powder in reaction equipment, wherein the density of the nano magnesium-based hydrogen storage alloy powder is 0.1-0.8g/cm3. When the powder is laid, the filling density of the powder is too high, so that the transmittance of mixed gas in the hydrogen absorption process is low, and the working efficiency of the system is further influenced; too low a packing density can result in too low a hydrogen recovery efficiency and can also result in gas flow carryover out of the powder.
The invention relates to application of nano magnesium-based hydrogen storage alloy powder, wherein the volume content of hydrogen in mixed gas is less than or equal to 99.999 percent.
According to the application of the nano magnesium-based hydrogen storage alloy powder, when the mass percentage of hydrogen in mixed gas is as low as 1-6%, the nano magnesium-based hydrogen storage alloy powder can well realize the separation of hydrogen from other gases.
The invention relates to the application of nano magnesium-based hydrogen storage alloy powder, wherein the pressure of mixed gas is 0.1-100bar before the nano magnesium-based hydrogen storage alloy powder enters reaction equipment.
The invention relates to application of nano magnesium-based hydrogen storage alloy powder, wherein the purity of collected hydrogen is more than or equal to 99.9999%.
The application of the nano magnesium-based hydrogen storage alloy powder provided by the invention is that the nano magnesium-based hydrogen storage alloy powder can be used for the next period after being heated to the temperature of B ℃ to release hydrogen. In the present invention, one cycle is to absorb and separate hydrogen and other gases, and then heat to release hydrogen. The cycle is repeated, i.e. a cycle is formed.
The invention discloses application of nano magnesium-based hydrogen storage alloy powder, wherein the mixed gas is preferably at least one of argon-hydrogen mixed gas, natural gas-hydrogen mixed gas, industrial 4N hydrogen and industrial 5N hydrogen. The purity of the hydrogen can be improved to 6N or even more than 6N by the treatment of the invention.
The invention relates to an application of nano magnesium-based hydrogen storage alloy powder, which comprises the following specific operation methods in large-scale industrial application: introducing hydrogen-containing mixed gas into the hydride reaction bed in a low-temperature interval, wherein valves 2 and 4 are opened, and a valve 6 is closed until the materials in the hydride reaction bed fully absorb hydrogen; then the reaction bed is heated to a high temperature range, at the moment, the valves 2 and 4 are closed, the valve 6 is opened, and the hydride is decomposed to release hydrogen with higher purity.
The hydrogen separation method provided by the patent adopts the cheap magnesium-based hydrogen storage alloy as the separation material, avoids the use of expensive Pd-based metal, and has better economic value. The method is simple and easy to implement, high in separation efficiency and good in application prospect.
The invention utilizes the magnesium-based hydrogen storage alloy to carry out selective chemical absorption on hydrogen at low temperature and decompose and release hydrogen at slightly high temperature. The method has low requirements on the pressure of the mixed gas and the hydrogen content of the gas, high purity of the obtained hydrogen, low energy consumption, simple process, safety and reliability. With the presence of O in the gas mixture2、CO、H2O、H2S and other impurities which are easy to cause oxidation and dirtying can be well removed.
Drawings
FIG. 1 is a schematic diagram of an apparatus for industrial application of the present invention.
FIG. 2 is a schematic diagram of the temperature and hydrogen absorption and desorption reactions of the continuous temperature cycle according to the present invention.
The basic principle and the basic structure of the device of the invention in industrial application can be seen from the attached figure 1.
The temperature dependence of successive temperature cycles can be seen in figure 2. Namely the reaction relationship of hydrogen absorption and desorption of the magnesium-based hydrogen storage alloy in the temperature cycle process.
Detailed Description
The present invention will be described in further detail with reference to examples.
The first embodiment is as follows:
1. magnesium-based hydrogen storage alloy powder (grain size is 10-100nm) is filled in the hydride reaction bed; after laying, the filling density is 0.1-0.3g/cm3The hydrogen-containing gas mixture consists of 50% hydrogen and 50% argon.
2. Continuous temperature circulation of 150-350 deg.c is applied to the hydride reaction bed, and the heating rate and cooling rate are both 10 deg.c/min.
3. Introducing hydrogen-containing mixed gas (pressure of 0.5bar) into the hydride reaction bed at the temperature of 150-199 ℃, opening the valves 2 and 4, closing the valve 6, and fully absorbing hydrogen in the magnesium-based hydrogen storage alloy at the stage; then the reaction bed is heated to a high temperature range of 200-350 ℃, at the moment, the valves 2 and 4 are closed, the valve 6 is opened, and the hydride is decomposed to release hydrogen with higher purity (the purity is 6N).
Example two:
1. the hydride reaction bed is filled with magnesium-based hydrogen storage alloy powder (grain size is 1-20nm) and laid, and the filling density is 0.1-0.2g/cm3The hydrogen-containing gas mixture consists of 5% hydrogen and 95% argon.
2. Continuous temperature circulation of 25-350 deg.c is applied to the hydride reaction bed, and the heating rate and cooling rate are both 5 deg.c/min.
3. Introducing hydrogen-containing mixed gas (pressure is 1bar) into the hydride reaction bed at the temperature of 25-200 ℃, opening the valves 2 and 4 at the moment, closing the valve 6, and fully absorbing hydrogen in the magnesium-based hydrogen storage alloy at the stage; then the reaction bed is heated to a high temperature range of 201-350 ℃, at the moment, the valves 2 and 4 are closed, the valve 6 is opened, and the hydride is decomposed to release hydrogen with higher purity (the purity is 6N).
Example three:
1. the hydride reaction bed is filled with magnesium-based hydrogen storage alloy powder (grain size is 1-20nm) and laid, and the filling density is 0.3-0.5g/cm3The hydrogen-containing mixed gas consists of 5 percent of hydrogen, 90 percent of argon and 5 percent of methane gas.
2. Continuous temperature circulation of 50-300 deg.c is applied to the hydride reaction bed, and the heating rate and cooling rate are both 10 deg.c/min.
3. Introducing hydrogen-containing mixed gas (pressure is 1bar) into the hydride reaction bed at the temperature of 50-200 ℃, opening the valves 2 and 4 at the moment, closing the valve 6, and fully absorbing hydrogen in the magnesium-based hydrogen storage alloy at the stage; then the reaction bed is heated to a high temperature range of 201-300 ℃, at the moment, the valves 2 and 4 are closed, the valve 6 is opened, and the hydride is decomposed to release hydrogen with higher purity (the purity is 6N and above).
Comparative example one:
1. the hydride reaction bed is filled with micron-sized magnesium-based hydrogen storage alloy powder (grain size is 10-100 μm) and laid, and the filling density is 0.5-1.0g/cm3The hydrogen-containing gas mixture consists of 5% hydrogen and 95% argon.
2. Continuous temperature circulation of 50-300 deg.c is applied to the hydride reaction bed, and the heating rate and cooling rate are both 10 deg.c/min.
3. Introducing hydrogen-containing mixed gas (pressure is 1bar) into the hydride reaction bed at the temperature of 50-200 ℃, opening the valves 2 and 4 at the moment, closing the valve 6, and ensuring that the magnesium-based hydrogen storage alloy does not have obvious hydrogen absorption reaction in the stage; then the temperature of the reaction bed is increased to a high temperature range of 201-300 ℃, at the moment, the valves 2 and 4 are closed, the valve 6 is opened, and hydrogen release is not obtained.
Claims (10)
1. The application of nano magnesium-based hydrogen storage alloy powder is characterized in that: the hydrogen is separated and/or purified from the hydrogen-containing mixed gas by taking nano magnesium-based hydrogen storage alloy powder as a separating and/or purifying agent.
2. The use of a nano magnesium-based hydrogen storage alloy powder according to claim 1, wherein: placing the nano magnesium-based hydrogen storage alloy powder in reaction equipment, and introducing hydrogen-containing mixed gas at the temperature of A ℃; then stopping introducing the hydrogen-containing mixed gas, and heating the temperature of the nano magnesium-based hydrogen storage alloy powder to B ℃; collecting hydrogen; a is less than or equal to 300; the value range of B is 200-500, and B is larger than A.
3. The use of a nano magnesium-based hydrogen storage alloy powder according to claim 1, wherein: the grain size of the nano magnesium-based hydrogen storage alloy powder is 1-500 nm.
4. Use of a nano magnesium-based hydrogen storage alloy powder according to claim 2, wherein: the nano magnesium-based hydrogen storage alloy powder is placed in reaction equipment, and the packing density of the nano magnesium-based hydrogen storage alloy powder is 0.1-0.8g/cm3。
5. The use of a nano magnesium-based hydrogen storage alloy powder according to claim 1, wherein: the volume content of hydrogen in the mixed gas is less than or equal to 99.999 percent.
6. Use of a nano magnesium-based hydrogen storage alloy powder according to claim 2, wherein: when the mass percentage of hydrogen in the mixed gas is as low as 1-6%, the nano magnesium-based hydrogen storage alloy powder can be well separated from other gases.
7. Use of a nano magnesium-based hydrogen storage alloy powder according to claim 2, wherein: the pressure of the mixed gas is 0.1-100bar before entering the reaction equipment.
8. Use of a nano magnesium-based hydrogen storage alloy powder according to claim 2, wherein: the purity of the collected hydrogen is more than or equal to 99.9999 percent.
9. Use of a nano magnesium-based hydrogen storage alloy powder according to claim 2, wherein: the temperature of the nano magnesium-based hydrogen storage alloy powder is raised to B ℃ to release hydrogen, and then the nano magnesium-based hydrogen storage alloy powder can be used for the next period. In the present invention, one cycle includes: absorbing and separating hydrogen and other gases, and then heating to release hydrogen; the cycle is repeated, i.e. a cycle is formed.
10. The use of a nano magnesium-based hydrogen storage alloy powder according to claim 1, wherein: the mixed gas is at least one of argon-hydrogen gas mixed gas, natural gas-hydrogen gas mixed gas, industrial 4N hydrogen gas and industrial 5N hydrogen gas. The purity of the hydrogen can be improved to 6N or even more than 6N by the treatment of the invention.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811418893.6A CN111217327A (en) | 2018-11-26 | 2018-11-26 | Application of nano magnesium-based hydrogen storage alloy powder |
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| CN201811418893.6A CN111217327A (en) | 2018-11-26 | 2018-11-26 | Application of nano magnesium-based hydrogen storage alloy powder |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115535961A (en) * | 2022-10-24 | 2022-12-30 | 云南电网有限责任公司电力科学研究院 | Hydrogen absorption and desorption device for hydrogen storage alloy and preparation method thereof |
| CN116477569A (en) * | 2023-05-26 | 2023-07-25 | 大连金煜新能源有限公司 | High-purity hydrogen purification and storage integrated method and system based on magnesium-based hydrogen storage material |
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2018
- 2018-11-26 CN CN201811418893.6A patent/CN111217327A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115535961A (en) * | 2022-10-24 | 2022-12-30 | 云南电网有限责任公司电力科学研究院 | Hydrogen absorption and desorption device for hydrogen storage alloy and preparation method thereof |
| CN115535961B (en) * | 2022-10-24 | 2024-03-19 | 云南电网有限责任公司电力科学研究院 | Hydrogen absorbing and releasing device for hydrogen storage alloy and preparation method thereof |
| CN116477569A (en) * | 2023-05-26 | 2023-07-25 | 大连金煜新能源有限公司 | High-purity hydrogen purification and storage integrated method and system based on magnesium-based hydrogen storage material |
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Application publication date: 20200602 |