CN107298429A - A kind of method of regeneration ZrCo base hydrogen isotope storage materials - Google Patents
A kind of method of regeneration ZrCo base hydrogen isotope storage materials Download PDFInfo
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- CN107298429A CN107298429A CN201710251317.6A CN201710251317A CN107298429A CN 107298429 A CN107298429 A CN 107298429A CN 201710251317 A CN201710251317 A CN 201710251317A CN 107298429 A CN107298429 A CN 107298429A
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- zrco
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- hydrogen isotope
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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
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- 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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Abstract
The invention discloses a kind of method of regeneration ZrCo base hydrogen isotope storage materials, it is that T, Hydrogen Vapor Pressure are that the min of 10 min ~ 300 is handled under conditions of P that ZrCo base hydrogen isotope storage materials to be regenerated are placed in into temperature, i.e. regeneration is completed, and described T, P relation are P(bar)0.005 × T of <(℃)- 2.71.It can not be used at relatively high temperatures the present invention overcomes existing ZrCo bases hydrogen isotope storage material, and occur the high deficiency of complicated ZrCo base hydrogen isotope storage materials regeneration technology after disproportionated reaction, hydrogen isotope recovery difficulty, regeneration cost, with the advantage that method is simple, regeneration effect is notable and regeneration cost is relatively low.
Description
Technical field
The present invention relates to hydrogen isotope storage and supply technical field, and in particular to one kind regeneration ZrCo bases hydrogen isotope storage
The method for depositing material.
Background technology
Drastically reduction and a kind of increasingly serious, reproducible clean energy resource of exploitation of environmental problem with fossil energy
Have become an extremely urgent task.Wherein, because fusion reactor is using hydrogen isotope gas as nuclear fuel, that is, combustion is passed through
Burn deuterium tritium plasma to discharge huge energy, but do not produce high-level waste, be a kind of excellent cleaning energy
Source, therefore receive paying close attention to for people.The ITER of design-build(ITER)It is poly- with the China established
Become engineering experimental reactor(CFETR)The first purpose be develop the clean energy resource., must due in fusion reaction stack operation
The scarcity and radioactivity of tritium must be added according to actual Run-time scenario is its supply or reclaims hydrogen isotope gas, therefore in reality
Realize that hydrogen isotope is safely and efficiently stored and supplied during the use of border, be fusion energy extensive development and the key of application.
There is radioactivity in view of tritium, compared to gaseous state, the banking system of liquid, solid-state is stored in security, high efficiency
And there is obvious advantage in terms of ease-to-operate, and be all the isotope of hydrogen in view of deuterium and tritium, thus hydrogen storage technology
Can also be used for the storage and supply of deuterium, tritium, and by solid metallic or alloy in lower temperature, inhale hydrogen compared with low hydrogen pressure or put
Hydrogen, you can realize the storage and supply of hydrogen isotope.Therefore, using the reversible characteristic for inhaling/putting hydrogen of metal hydride, selection is closed
Suitable hydride, you can carry out solid hydrogen isotope(Protium, deuterium, tritium)Safe storage, defeated transfer, pump, purifying and trapping.
Material when ZrCo based alloys are due to low equilibrium dissociation pressure, fast hydrogen-absorption speed, non-core, low spontaneous combustion and storage tritium
The stability of material, has become the important candidate materials of hydrogen isotope storage and supply in ITER designs.However, the present application
People has been found that it puts hydrogen in multiple suction during ZrCo based alloys are used for hydrogen isotope processing(H、D、T)It can be sent out after circulation
Raw disproportionated reaction(2ZrCo + H2 → ZrH2 + ZrCo 2, 2ZrCoH3 → ZrH2 + ZrCo 2 + 2H2), due to ZrH2
Decomposition temperature(700 DEG C of >)It is more much higher than ZrCo hydride, ZrCo under normal conditions 2Also will not occur suction/hydrogen discharge reaction,
The notable delay of hydrogen isotope thus can be caused, the reversible suction of ZrCo alloys/put hydrogen capacity, dynamics and cycle performance hair is caused
Raw deep fades, cause its hydrogen storage property to deteriorate, therefore need to enter the ZrCo based alloys after disproportionation in actual use
Row regeneration treatment, makes it be re-converted into ZrCo alloy states from disproportionation state, so as to recover the ability of its hydrogen isotope storage.
The experimental results are it is disclosed that determine whether ZrCo based alloys are disproportionated and are disproportionated the key factor of degree
For temperature and hydrogen pressure.In general, temperature is higher or hydrogen pressure is higher, and easier induction ZrCo is disproportionated.For example, Shim etc.
Research shows(Shim M, Chung H, Cho S, Yoshida H. Disproportionation
characteristics of a zirconium-cobalt hydride bed under ITER operating
conditions [J]. Fusion Sci Technol, 2008, 53: 830-840.), when temperature is higher than 350 DEG C, hydrogen pressure
ZrCo based alloys will be very sensitive to disproportionation during more than 3.1 kPa.Therefore, in order to avoid ZrCo based alloys from being disproportionated as far as possible,
All it is controlled under lower temperature and uses in actual application, but this can accordingly cause hydrogen desorption capacity and the deflation of ZrCo based alloys
Speed is relatively low, and the application and popularization to ZrCo based alloys are very unfavorable.
And the research that regenerates has had a more report after being disproportionated for ZrCo based alloys, but substantially use is all high temperature
The method vacuumized.For example, Konishi etc. has found by experiment(Konishi S, Nagasaki T, Okuno K.
Reversible disproportionation of ZrCo under high temperature and hydrogen
pressure [J]. J Nucl Mater, 1995, 223: 294.), when disproportionation generation ZrH occurs for ZrCo2And ZrCo 2Afterwards,
A few houres are vacuumized at 500 DEG C can realize regeneration, and ZrCo alloys are reduced to again.Devillers etc. also uses same side
Method has carried out the regeneration research of ZrCo based alloys(Devillers M, Sirch M, Penzhorn RD. Hydrogen-
induced disproportionation of the intermetallic compound ZrCo [J]. Chemistry
of Materials, 1992, 4: 631.), they are pointed out, ZrCo conjunctions can be recovered by vacuumizing 2 h after ZrCo disproportionations at 500 DEG C
The shape of hydrogen storage capacity and PCI curves before gold disproportionation.Although currently used high temperature vacuum pumping method can also realize ZrCo
The regeneration of based alloy, but the mode vacuumized can cause the hydrogen isotope of vacuum pumped(Especially tritium)Reclaim difficult, simultaneously
Also the radwastes such as the pump that is polluted by tritium can be increased.
The content of the invention
The invention aims to overcome existing ZrCo bases hydrogen isotope storage material to use at relatively high temperatures,
And occur complicated ZrCo base hydrogen isotope storage materials regeneration technology after disproportionated reaction, hydrogen isotope recovery difficulty, regeneration cost
There is provided a kind of method of regeneration ZrCo base hydrogen isotope storage materials for high deficiency.
To achieve the above object, the technical solution adopted by the present invention is as follows:
A kind of method of regeneration ZrCo base hydrogen isotope storage materials, i.e., put ZrCo base hydrogen isotope storage materials to be regenerated
It is that T, Hydrogen Vapor Pressure are that the min of 10 min ~ 300 is handled under conditions of P in temperature, i.e. regeneration is completed;
Described T, P relation are P 0.005 × T-2.71 of <,
Wherein, T unit for DEG C, P unit is bar.
Specifically, the ZrCo bases hydrogen isotope storage material is ZrCo based alloys.
Specifically, the ZrCo based alloys are that the ZrCo bases binary with ZrCo phase crystal structures, ternary or quaternary are closed
Gold.
In particular, the ZrCo base hydrogen isotopes storage material to be regenerated includes being disproportionated in use
ZrCo based alloys and the ZrCo based alloys that are disproportionated using finishing.
Also, the hydrogen isotope includes any one or more in hydrogen, deuterium, tritium.
It is preferred that, the Hydrogen Vapor Pressure P is 0.05 ~ 3bar.
Compared with prior art, the invention has the advantages that:
Reclaim tired instant invention overcomes the complexity of the ZrCo based alloys regeneration technology after disproportionated reaction in the prior art, hydrogen isotope
It is difficult, the shortcomings of cost is high, and ZrCo based alloys can be overcome because avoiding being disproportionated and can not using at relatively high temperatures not
Foot, with the advantage that method is simple, regeneration effect is notable and regeneration cost is relatively low.
The inventive method can effectively realize the regeneration of ZrCo based alloys under conditions of not vacuumizing, and ensure that ZrCo
The use of based alloy at relatively high temperatures can avoid using vacuum so as to have very fast hydrogen discharging rate and higher hydrogen desorption capacity
Pump, reduces equipment investment cost.The inventive method is for promoting ZrCo based alloys in the application of hydrogen isotope storage art and pushing away
Extensively, have great importance.
Brief description of the drawings
Fig. 1 is FB(flow block) of the present invention.
Fig. 2 is the hydrogen pressure and temperature variation curve of disproportionation stage and regeneration stage in embodiment 1;
Fig. 3 is the XRD spectrum after being disproportionated in embodiment 1;
Fig. 4 is the XRD spectrum after regenerating in embodiment 1;
Fig. 5 is the hydrogen pressure and temperature variation curve of disproportionation stage and regeneration stage in embodiment 2;
Fig. 6 is the XRD spectrum after being disproportionated in embodiment 2;
Fig. 7 is the XRD spectrum after regenerating in embodiment 2.
Embodiment
The invention will be further described with embodiment for explanation below in conjunction with the accompanying drawings, and mode of the invention includes but not only limited
In following examples.
Following examples are for providing the regeneration that a kind of method is simple, regeneration effect is notable and regeneration cost is relatively low
The method of ZrCo base hydrogen isotope storage materials, as shown in figure 1, this method is that ZrCo bases hydrogen isotope to be regenerated is stored into material
It is that T, Hydrogen Vapor Pressure are that the min of 10 min ~ 300 is handled under conditions of P that material, which is placed in temperature,;Described T, P relation are P(bar)
0.005 × T of <(℃)- 2.71.Described in its specific implementation process following examples.
Embodiment 1
(1)The processing of ZrCo based alloys disproportionation:Load Sievert type test systems after first the ZrCo based alloys after activation are weighed
In reactor, 1 bar initial hydrogen pressure then will be filled with reactor, then reactor heats up with 2 DEG C/min heating rate
ZrCo based alloys can be disproportionated to 650 DEG C, obtain being disproportionated sample.
Meanwhile, it also can obtain hydrogen pressure and the temperature variation curve in the whole dismutation of ZrCo based alloys in reactor(I.e.
The hydrogen pressure and temperature variation curve in ZrCo based alloys disproportionation stage), as shown in Fig. 2 also, as seen from Figure 2, heating up
Hydrogen pressure in journey reactor, which first rises, then occurs in that decline, presents the notable feature that ZrCo based alloys are disproportionated;
Disproportionation sample is subjected to XRD analysis, obtains being disproportionated the XRD spectrum of sample, as shown in figure 3, and as seen from Figure 3
ZrCo based alloys have been completely transformed into ZrH2And ZrCo 2;
(2)The regeneration of ZrCo based alloys after disproportionation:The reactor that will be equipped with sample is continually maintained in 650 DEG C, and hydrogen pressure is adjust and reform
For 0.2 bar, 180 min, i.e. completion regenerate under the conditions of reactor then is maintained at into the temperature, hydrogen pressure, obtain regenerating sample.
Wherein, the relation of hydrogen pressure and temperature meets 0.2 0.005 × 650-2.71 of < in the regeneration technology of the ZrCo based alloys after disproportionation
=0.54;
Meanwhile, it also can obtain hydrogen pressure and the temperature variation curve in the whole regenerative process of ZrCo based alloys in reactor(That is ZrCo
The hydrogen pressure and temperature variation curve of based alloy regeneration stage), as shown in Fig. 2 also, as seen from Figure 2, the time required to regeneration
It is shorter, and finally present the notable feature that the regeneration of ZrCo based alloys is finished;
Regeneration sample is subjected to XRD analysis, obtains regenerating the XRD spectrum of sample, as shown in figure 4, also, being can be found that by Fig. 4
Sample after regeneration is substantially completely converted into ZrCo based alloys.
Embodiment 2
In the present embodiment, except(2)Hydrogen pressure in step in reactor is adjust and reform is outside 200 min for 0.3bar, regenerative response time,
Remaining is same as Example 1.
In the present embodiment, by step(1)The hydrogen pressure and temperature variation curve record in obtained ZrCo based alloys disproportionation stage
As shown in figure 5, the XRD spectrum record for obtaining being disproportionated sample is as shown in Figure 6;Also, by step(2)In obtained ZrCo based alloys
The hydrogen pressure and temperature variation curve of regeneration stage recorded among Fig. 5, and the XRD spectrum record for obtaining being disproportionated sample is as shown in Figure 7.
Embodiment 3
(1)The processing of ZrCo based alloys disproportionation:Load Sievert type test systems after first the ZrCo based alloys after activation are weighed
In reactor, 2 bar initial hydrogen pressure then will be filled with reactor, then reactor heats up with 5 DEG C/min heating rate
ZrCo based alloys can be disproportionated to 600 DEG C, obtain being disproportionated sample.
(2)The regeneration of ZrCo based alloys after disproportionation:The reactor that will be equipped with sample is continually maintained in 600 DEG C, by hydrogen pressure
Adjust and reform as 0.1 bar, reactor is then maintained at 150 min under the conditions of the temperature, hydrogen pressure, that is, completes regeneration, is regenerated
The ZrCo based alloys finished.Wherein, the relation of hydrogen pressure and temperature meets 0.1 < in the regeneration technology of the ZrCo based alloys after disproportionation
0.005 × 600-2.71=0.29;
Embodiment 4
The step of the present embodiment(1)It is same as Example 3, step(2)It is as follows:
The regeneration of ZrCo based alloys after disproportionation:The reactor that will be equipped with sample is continually maintained in 590 DEG C, by hydrogen pressure adjust and reform for
0.05 bar, 190 min, i.e. completion regenerate under the conditions of reactor then is maintained at into the temperature, hydrogen pressure, obtain regenerating what is finished
ZrCo based alloys.Wherein, the relation of hydrogen pressure and temperature meets 0.05 < 0.005 in the regeneration technology of the ZrCo based alloys after disproportionation
× 590-2.71=0.24.
From above-described embodiment, the ZrCo base hydrogen isotope storage material renovation process of the inventive method is authentic and valid,
And with the advantage that method is simple and regeneration cost is relatively low, meanwhile, effectively it can realize ZrCo bases under conditions of not vacuumizing
The regeneration of alloy, ensure that the use of ZrCo based alloys at relatively high temperatures with very fast hydrogen discharging rate and higher to put hydrogen
Amount, and can avoid occurring tritium pollution vavuum pump so as to produce the situation generation of the Spent Radioactives such as pump, reduce equipment cost
Input.In addition, the ZrCo based alloy favorable regeneration effects after being disproportionated it can be seen from Fig. 2 ~ Fig. 5, are substantially completely converted into ZrCo bases
Alloy;Also, whole regenerative process is time-consuming to be less than 100min, and regeneration effect is best at the beginning for regeneration, in temperature identical situation
Under, pressure is lower, and reproduction speed is faster.
Above-described embodiment is only the preferred embodiment of the present invention, should not be taken to limit protection scope of the present invention, but
It is all the present invention body design thought and mentally make have no the change of essential meaning or polishing, its technology solved
Problem is still consistent with the present invention, should be included within protection scope of the present invention.
Claims (6)
1. a kind of method of regeneration ZrCo base hydrogen isotope storage materials, it is characterised in that by the same position of ZrCo base hydrogen to be regenerated
It is that T, Hydrogen Vapor Pressure are that the min of 10 min ~ 300 is handled under conditions of P that plain storage material, which is placed in temperature, i.e. regeneration is completed;
Described T, P relation are P 0.005 × T-2.71 of <,
Wherein, T unit for DEG C, P unit is bar.
2. the method for a kind of regeneration ZrCo base hydrogen isotope storage materials according to claim 1, it is characterised in that described
ZrCo base hydrogen isotopes storage material is ZrCo based alloys.
3. the method for a kind of regeneration ZrCo base hydrogen isotope storage materials according to claim 2, it is characterised in that described
ZrCo based alloys are ZrCo bases binary, ternary or quaternary alloy with ZrCo phase crystal structures.
4. a kind of method of regeneration ZrCo bases hydrogen isotope storage material according to claim 1 ~ 3 any one, it is special
Levy and be, the ZrCo base hydrogen isotopes storage material to be regenerated includes the ZrCo based alloys being disproportionated in use
With the ZrCo based alloys being disproportionated using finishing.
5. the method for a kind of regeneration ZrCo base hydrogen isotope storage materials according to claim 4, it is characterised in that described
Hydrogen isotope includes any one or more in hydrogen, deuterium, tritium.
6. a kind of method of regeneration ZrCo base hydrogen isotope storage materials according to claim 1 or 5, it is characterised in that
The Hydrogen Vapor Pressure P is 0.05 ~ 3bar.
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Publication number | Priority date | Publication date | Assignee | Title |
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CN109371374A (en) * | 2018-11-14 | 2019-02-22 | 中国工程物理研究院材料研究所 | A kind of the ZrCo base storage tritium material and preparation method of membrane structure |
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CN101100285A (en) * | 2006-07-07 | 2008-01-09 | 中国科学院金属研究所 | Chemical hydride hydrogen storing material system, hydrogen preparing method and hydrogen preparing device |
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CN1836055A (en) * | 2003-04-01 | 2006-09-20 | 双向电池公司 | Low temperature alkaline fuel cell |
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