GB2219948A - A method for refining hydrogen gas using a storage alloy - Google Patents
A method for refining hydrogen gas using a storage alloy Download PDFInfo
- Publication number
- GB2219948A GB2219948A GB8903276A GB8903276A GB2219948A GB 2219948 A GB2219948 A GB 2219948A GB 8903276 A GB8903276 A GB 8903276A GB 8903276 A GB8903276 A GB 8903276A GB 2219948 A GB2219948 A GB 2219948A
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- GB
- United Kingdom
- Prior art keywords
- hydrogen gas
- alloy
- hydrogen
- storage alloy
- gas
- 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.)
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
-
- 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
-
- 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
- C01B3/508—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by selective and reversible uptake by an appropriate medium, i.e. the uptake being based on physical or chemical sorption phenomena or on reversible chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/16—Hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
- B01D53/053—Pressure swing adsorption with storage or buffer vessel
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Gas Separation By Absorption (AREA)
Description
A METHOD FOR REFU41NG HYDROGEN GAS 2219948 2
BACKGROUND OF THE RTVENTI
3 4 This invention relates to a method for refining a high purity hydrogen gas by absorbing a hydrogen gas into a hydrogen 6 storage alloy, more particularly, adsorbing impurity gases 7 contained in hydrogen gas by using the hydrogen storage alloy 8 which represents Ti(,-x)ZrxMnO.8CrlCUO.2 wherein x is 0.01:5 X:5 0.5.
9 [Prior Art]
It is known that the storage alloy are having hydrogen storage ability, to which a hydrogen gas were absorbed, at the 12 C 13 same time impurity gases such as nitrogen gas, methane gas 14 contained in hydrogen gas were adsorbed. And that said impurity gases once adsorbed into the hydrogen storage alloy are 16 not desorbed, therefore, so that desorbed hydrogen gas contained no impurities can be obtained.
17 The hydrogen storage alloys used in said prior art
18 19 include one-component system alloys such as Ca, Li, K, Ti, V, Mg, I i or a rare earth element alloy (R), two-component system alloys such as TiMnl.5, TiFe, LaNi5, MgNi2 or TiCo-alloy, and multi 21 component system alloys such as TiZrMg, TiFeMn, R-ZrCo or 22 CoNiMg-alloy. Above all, a TiMn-alloy is very effective in 23 24 separation and purification of impurity gases, especially of nitrogen.
26 Said hydrogen storage alloy have, however, 27 disadvantages that the amount of absorbed hydrogen gas 28 decreases as the accumulative amount of adsorbed impurity gases 29 such as nitrogen gas, methane gas increases, by repeated use of the hydrogen storage alloy in order to refine a hydrogen gas, C 2 I therefore said alloys can not be used for a long life because of 9 their decreased adsorption capability of impurity gases. Also, 3 said hydrogen storage alloy have disadvantage that some of 4 hydrogen storage alloys are high pressure when hydrogen gas is absorbed or desorbed so that their are unhandy, and that their 6 hysteresis is generally wide.
7 It is therefore an object of the present invention to 8 improve the disadvantages of said conventional alloys. It is 9 another object of the present invention to provide a method for hydrogen gas using a hydrogen storage alloy whose absorbed 10 11 amount of hydrogen and the adsorption capability of nitrogen 12 lower less and which is handy.
13 The present invention relates to a method for hydrogen 14 gas wherein hydrogen gas containing nitrogen gas is supplied to a hydrogen storage alloy expressed in Ti(,-,X)ZrxMnO.8Cr,CUO.2 b 16 (wherein X is 0.01:!- X:5 0.5), the hydrogen storage alloys is 17 saturated with hydrogen by absorption, then impurity gases such 18 as nitrogen, etc. contained in hydrogen gas are adsorbed to the 19 hydrogen storage alloy. Hydrogen gas is desorbed from the hydrogen storage alloy and the desorbed hydrogen gas containing 20 21 no impurity gases such as nitrogen, etc. is recovered.
22 The Ti(,-x)ZrxMno.8Cr,CUO.2 hydrogen storage alloy used in 23 the present invention is characteristic of its low hysteresis. In 24 addition, as described in the following, said alloy can be used for a long time under a stable condition since the amount of absorbed 26:i hydrogen gas decreases less compared with said conventional 27 alloys even when said alloy is a number of repeated, and since 28 accumulatively adsorbed impurity gases such as nitrogen, etc.
29 result in less lowering of its adsorption capability.
The hydrogen storage allcy to be used in this invention are formed in tablet or packed in can with ground particles from 2 3 melted ingot.
4 In the completely same manner for the conventional alloys, the hydrogen storage alloy used in the present invention is 6 c-ooled when absorbing hydrogen, and is heated when desorbing 7 hydrogen. Thus, the alloy of the present invention is handy for 8 absorption and desorption at pressure of 4 - 10 atm.
9 BRIEF DESCRTPTION OF THE DRAWINGS 11 Figure 1 is a flow sheet of one embodiment of the 12 present invention; 13 Figure 2 is a graph showing the purification 14 characteristics of the TiMnj.2Cr0.2 alloy; Figure 3 is a graph showing the purification 16 characteristics of the Tio.77Mno.8Zr0.23CrjCU0.2 alloy; Figure 4 is a graph showing the adsorption performance 17 is of the TiMn,.2CrO.2 alloy after the repeated tests; and 19 Figure 5 is a graph showing the adsorption performance of the Tio.77Mno.sZr0.23CrjCu0.2 alloy after the repeated tests.
21 22 DESCRTPTION OF THE PREFERRED EMBODIMENTS 23 One embodiment of the present invention is shown in 24 Figure I as a flow sheet. A hydrogen gas are taken out by released a valve (Vl) of materials of a hydrogen gas cylinder, 26 which are storaged by introduction of 200 g of hydrogen storaged
I alloy packed container (C) through mass flow meter (F), and then, 27 28 another valve (V2) are released and a hydrogen gas are desorbed.
Simultaneously, desorbed hydrogen gas are placed for analysis by gas chromatography (GC PID) after desorb rate are controlled by 0 4 I mass flow controller (MFC) at flow amount.f 200 cc/min. Such 2 described method are used for comparative tests of a hydrogen 3 storaged alloy as following:
4 1. Purification characteristics comparison experim ent; 6 One comparison example of the purification characteristics of one embodiment (Ti0.77Mno.gZro.23Cr1CU0.2) of the 7 8 -hydrogen storage alloys according to the present invention and an 9 alloy (TiMnj.2Cr0.2) is shown in Figs. 2 and 3.
11 Experiment method; 12 Ti0.77Mno.8Zr0.23Cr1CU0.2 alloy 13 Amount of alloy 200 g 14 Activation condition After one-hour exhaust (R/P, 300C), the absorption and 16 desorption of H2 of 30 atm are 17 repeated at a temperature of 18 30'C for 3 cycles.
19 Measurement condition Absorption and desorption temperature 30'C; Absorbed 21 gas H2 (N2: 10.5 ppm) 10 atm.
22 Desorption method Without purge: Desorption 23 speed 200 cc/min. constant.
24 Measurement points 0.4, 4, 8, 12, 16, 20 (lit.) TiMn1.2Cr0.2 alloy 26 Amount of alloy 200 g 27 Activation condition After one-hour heated exhaust 28 (R/P, 800C), the absorption and 29 desorption of H2 of 35 atm are I:epeated at a tem --raturc of 2 40'C for 5 cycles.
3 Measurement condition Absorption and desorption 4 temperature 40'C; absorbed gas H2 (N2: 10.5 ppm) 10 atm.
6 Desorption method Without purge: Desorption 7 speed 200 cc/min. constant.
8 Measurement points 0.4, 4, 8, 12, 16, 20 (lit.) 9 As seen from Figures 2 and 3, in both cases only CI44 is detected when 0.4 lit. of hydrogen has been-desorbed which 11 12 means that 99% of six-nine purity (99.9999) hydrogen is 13 recovered. The dashed lines in Figures 2 and 3 indicate the 14 detection limit values of the analyzing apparatus (GC), and the actual values lie therefore below the dashed lines (The same may 16 be said of Figures 4 and 5).
17 18 2. Comparison of the adsorption performance after the repeated 19 tests:
Using the two kinds of hydrogen storage alloys used in said tests, the absorption and desorption of H2 containing 3040 21 q !I ppm of N2 was repeated 10 times. Said test condition corresponds 22 23 to the 3000 times; repeated absorption and desorption of 99% of 24 four-nine purity (99.99) hydrogen (N2-content: 10.5 ppm).
For the TiMnI.2CrO.2 alloy the cycle mode of absorption 26 and desorption comprises 30 minutes of absorption time. 1 27 minute of holding time, and 50 minutes of desorption time, and 28 for the TiO.77Mno.8ZrO.23CrjCUO.2 alloy it comprises 40 minutes of 29 absorption time, 50 minutes of holding time, and 30 minutes of 1 desorption time. In Figures 4 and 5 one example of the 2 adsorption performance is shown respectively.
3 As shown Figure 4, the alloy comprising TiMnl.2Cro.2 4 detected N2, and it was confirmed that the concentration of this N2 did contain 9 ppm in the desorbed hydrogen gas at desorbed flow 6 amount of a hydrogen gas of over 5 lit.
7 Compared with this, the alloy according to the present 8 invention resulted as shown in Figure 5 that a hydrogen gas 9 desorption amount around 5 lit. detected approximately 2 ppm. N2 of concentration and it was further recognized that the 11 concentration of N2 contained only approximately 3 pprn in the 12 desorption amount of a hydrogen gas of over 10 lit.
13 The alloy used in the present invention, even after 14 repeated usage, is less decrease of impurity gases adsorption capability compared with TiMnj.2CrO.2. so that, the alloy of the 16 present invention can be improve the impurity gases adsorption 17 capability.
18 When analyzing the hydrogen gas absorbed, held for 2 19 3 hours and desorbed by the alloy used in the present invention, no N2 was detected, and 99% recovery was obtained again. This 21 fact means that the alloy used in the present invention can regain the adsorption capability by absorbing hydrogen and prolonging 22 23 its holding time.
24 26 27 28 29 7
Claims (1)
- I CLAIMA method for refining a high purity hydrogen gas by absorbing a hydrogen gas into a hydrogen storage alloy, desorbing 4 high purity hydrogen gas by adsorbing impurity gases contained in a hydrogen gas by using said hydrogen storage alloy which 6 representsTi(,-x)ZrxMno.sCr,CUO.2 wherein x is 0.01:5z:5 0.5.7 8 11 12 13 14 17 18 19 20 21 22 23 24 25 26 27 28 29 Published 1989 at The Patent Office. State House. 6671 High Holborn. London WCIR4TPParther copies maybe obtained from The -Patent Office.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63158962A JPH029701A (en) | 1988-06-27 | 1988-06-27 | Method for purifying hydrogen |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8903276D0 GB8903276D0 (en) | 1989-04-05 |
| GB2219948A true GB2219948A (en) | 1989-12-28 |
| GB2219948B GB2219948B (en) | 1992-09-30 |
Family
ID=15683163
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8903276A Expired - Lifetime GB2219948B (en) | 1988-06-27 | 1989-02-14 | A method for refining hydrogen gas |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPH029701A (en) |
| DE (1) | DE3906314A1 (en) |
| FR (1) | FR2633194B1 (en) |
| GB (1) | GB2219948B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2671338A1 (en) * | 1989-10-30 | 1992-07-10 | Gni | Process for obtaining a gaseous nitrogen/hydrogen mixture for the synthesis of ammonia |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2686466B2 (en) * | 1990-10-05 | 1997-12-08 | 大陽東洋酸素株式会社 | Method and apparatus for analyzing trace impurities in nitrogen gas |
| CN107739859B (en) * | 2017-10-27 | 2019-12-10 | 中国工程物理研究院流体物理研究所 | preparation process of hydrogen storage crack-free zirconium-titanium-copper alloy electrode source sheet |
| CN109908892A (en) * | 2017-12-12 | 2019-06-21 | 中国科学院大连化学物理研究所 | A kind of ultra-pure hydrogen purifying sorbent material and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53146910A (en) * | 1977-05-10 | 1978-12-21 | Matsushita Electric Ind Co Ltd | Hydrogen storing material |
-
1988
- 1988-06-27 JP JP63158962A patent/JPH029701A/en active Pending
-
1989
- 1989-02-09 FR FR8901701A patent/FR2633194B1/en not_active Expired - Fee Related
- 1989-02-14 GB GB8903276A patent/GB2219948B/en not_active Expired - Lifetime
- 1989-02-28 DE DE3906314A patent/DE3906314A1/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2671338A1 (en) * | 1989-10-30 | 1992-07-10 | Gni | Process for obtaining a gaseous nitrogen/hydrogen mixture for the synthesis of ammonia |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH029701A (en) | 1990-01-12 |
| FR2633194B1 (en) | 1993-04-09 |
| GB8903276D0 (en) | 1989-04-05 |
| GB2219948B (en) | 1992-09-30 |
| FR2633194A1 (en) | 1989-12-29 |
| DE3906314A1 (en) | 1989-12-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19940214 |