CN115626608B - Zr is confirmed fast 2 Method for resisting poisoning temperature of Fe-based alloy and method for improving poisoning resistance - Google Patents
Zr is confirmed fast 2 Method for resisting poisoning temperature of Fe-based alloy and method for improving poisoning resistance Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 72
- 239000000956 alloy Substances 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 52
- 230000000607 poisoning effect Effects 0.000 title abstract description 17
- 231100000572 poisoning Toxicity 0.000 title abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 50
- 239000001257 hydrogen Substances 0.000 claims abstract description 48
- 239000007789 gas Substances 0.000 claims abstract description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000012535 impurity Substances 0.000 claims abstract description 36
- 238000010521 absorption reaction Methods 0.000 claims abstract description 27
- 229910052722 tritium Inorganic materials 0.000 claims abstract description 23
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 claims abstract description 21
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims abstract description 8
- 229910052805 deuterium Inorganic materials 0.000 claims abstract description 8
- 230000001568 sexual effect Effects 0.000 claims abstract description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 20
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 19
- 230000001147 anti-toxic effect Effects 0.000 claims description 13
- 238000001179 sorption measurement Methods 0.000 claims description 13
- 238000004364 calculation method Methods 0.000 claims description 11
- 238000003775 Density Functional Theory Methods 0.000 claims description 10
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229910002059 quaternary alloy Inorganic materials 0.000 claims description 4
- 229910002058 ternary alloy Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910002056 binary alloy Inorganic materials 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 238000001784 detoxification Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 8
- 238000012360 testing method Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000004904 shortening Methods 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 19
- 230000004927 fusion Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-PWCQTSIFSA-N Tritiated water Chemical compound [3H]O[3H] XLYOFNOQVPJJNP-PWCQTSIFSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000002285 radioactive effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910015136 FeMn Inorganic materials 0.000 description 1
- 241001124320 Leonis Species 0.000 description 1
- 206010029350 Neurotoxicity Diseases 0.000 description 1
- 244000089486 Phragmites australis subsp australis Species 0.000 description 1
- 206010044221 Toxic encephalopathy Diseases 0.000 description 1
- 229910008008 ZrCo Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 231100000025 genetic toxicology Toxicity 0.000 description 1
- 230000001738 genotoxic effect Effects 0.000 description 1
- 231100000386 immunotoxicity Toxicity 0.000 description 1
- 230000007688 immunotoxicity Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000228 neurotoxicity Toxicity 0.000 description 1
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- 238000011056 performance test 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C16/00—Alloys based on zirconium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2202/00—Physical properties
- C22C2202/04—Hydrogen absorbing
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- 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
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/10—Nuclear fusion reactors
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Abstract
The invention provides a method for rapidly determining Zr 2 Method for improving poisoning temperature of Fe-based alloy and Zr 2 A method for the anti-poisoning performance of Fe-based alloy relates to the technical field of hydrogen isotope storage. The invention predicts Zr by theory of first sexual principle 2 The Fe-based alloy has the advantages of resisting the poisoning condition of impurity gas, greatly shortening the time and the raw material cost of experimental test, along with universal applicability and outstanding effect. The invention can avoid or relieve Zr 2 Impurity poisoning problem of Fe-based alloy in hydrogen/deuterium/tritium absorption process, thereby improving Zr 2 Fe-based hydrogen absorption properties.
Description
Technical Field
The invention relates to the technical field of hydrogen isotope storage, in particular to a method for quickly determining Zr 2 Method for improving poisoning temperature of Fe-based alloy and Zr 2 A method for preparing Fe-based alloy with anti-poisoning performance.
Background
With the development of human society, energy crisis is increasingly remarkable. As a large country of energy consumption, china is required to keep economic sustainable development and solve the problem of environmental pollution, and has urgent need for clean and renewable new energy. Among a plurality of novel energy sources, the controllable fusion energy with small external influence and high safety and high energy density becomes an ideal way for solving the energy crisis. Currently, the research of magnetic confinement fusion based on tokamak device is relatively extensive and rapid in progress. As the preferred scheme of the international thermonuclear fusion experimental reactor, deuterium-tritium fusion reaction is the fusion reaction path which is most easily realized. However, since tritium itself is both fuel and radioactive, it is not only very expensive, but also can cause significant environmental pollution once leaked. Therefore, tritium control is a very important issue for fusion stacks fuelled with deuterium-tritium.
One well-established method for tritium removal is to collect the tritium-containing waste gas as tritium water after catalytic oxidation. However, tritiated water can enter the nucleus/cell to produce biological effects including genotoxicity, immunotoxicity, neurotoxicity. Thus, tritiated water is extremely toxic compared to radioactive tritium gas, and can cause greater contamination even at low concentrations. At present, the metal getter method is used for capturing tritium in inert atmosphere, so that the method has the advantages of no generation of highly toxic tritium water, easy recovery of captured tritium and the like, and is a method for treating tritium-containing waste gas which is greatly developed in the current tritium process laboratory.
Zr 2 The Fe alloy can achieve higher absorption efficiency on hydrogen under the condition of lower hydrogen content concentration, and the raw material cost is lower than that of other zirconium-based alloys, such as ZrCo, zrNi and the like, thus Zr 2 Fe alloy has wide application in practical industrial production. However, the impurity gas naturally exists in the air or is generated by a tritium recovery system, and the poisoning of the gas can seriously obstruct Zr 2 Fe in tritium technology, so that the anti-poisoning capability is to evaluate Zr 2 One key parameter of Fe alloys. At present, zr is related to impurity gases (such as carbon monoxide) 2 The study of the performance decay of Fe alloy in the hydrogen absorption process is rarely reported, and only Prigent et al characterize Zr 2 Fe alloy vs. pure hydrogen and 5vol.% CO+95vol.% H 2 The gas adsorption properties of the mixture show that low concentration of CO at room temperature reduces Zr 2 The hydrogen absorption properties of Fe alloys are still evident over a longer time scale (Prigent, j.; latroche, m.; leoni, e.; rohr, v.; hydrogen trapping properties of Zr-based intermetallic compounds in the presence of CO contaminant gas. Journal of alloys and compounds 2011,509, S801-S803.). At present, if each temperature is considered in the experimental means for exploring the influence of impurity gas on the hydrogen absorption performance of the zirconium-based alloy, the time consumption is long, the efficiency is low, and the optimal temperature of the zirconium-based alloy in practical application cannot be rapidly judged.
Disclosure of Invention
The invention aims to provide a method for quickly determining Zr 2 Method for improving poisoning temperature of Fe-based alloy and Zr 2 The method for determining the poisoning resistance of the Fe-based alloy can rapidly determine the optimal temperature of the Zr-based alloy in practical application and improve Zr 2 Resistance to poisoning of Fe-based alloys.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for rapidly determining Zr 2 A method for detoxifying an Fe-based alloy comprising the steps of: calculation of impurity gas in Zr according to density functional theory of first sexual principle 2 The number of saturated adsorption molecules on the surface of the Fe-based alloy;
thermodynamic calculation based on first principle to adsorb impurity gas with different molecular numbers in Zr 2 Gibbs free energy of the Fe-based alloy surface as a function of temperature;
the Gibbs free energy of the impurity gas with different molecular numbers is used as Zr at a temperature which is more than or equal to 0 2 The antitoxic temperature of the Fe-based alloy.
Preferably, the impurity gas includes one or more of carbon monoxide, oxygen and carbon dioxide.
The invention provides a method for improving Zr 2 A method for detoxifying an Fe-based alloy comprising the steps of:
determination of Zr according to the method described in the above scheme 2 The antitoxic temperature of the Fe-based alloy;
zr is made to be 2 The Fe-based alloy absorbs hydrogen at the antitoxic temperature.
Preferably, the Zr 2 The Fe-based alloy is provided with Zr 2 Zr of Fe phase crystal structure 2 One or more of Fe-based binary, ternary and quaternary alloys.
Preferably, the pressure of the hydrogen absorption is 1bar.
Preferably, before the hydrogen absorption, the method further comprises the step of preparing Zr 2 The Fe-based alloy is activated, wherein the activation temperature is 400 ℃ and the activation time is 2h.
Preferably, the hydrogen-absorbing gas comprises hydrogen, deuterium gas or tritium gas, or hydrogen formed by any two isotopes of hydrogen, deuterium and tritium.
Preferably, the Zr 2 The particle size of the Fe-based alloy is 70-120 meshes, and the purity is high>99％。
The invention provides a method for rapidly determining Zr 2 A method for detoxifying an Fe-based alloy comprising the steps of: calculation of impurity gas in Zr according to density functional theory of first sexual principle 2 The number of saturated adsorption molecules on the surface of the Fe-based alloy; thermodynamic calculation based on first principle to adsorb impurity gas with different molecular numbers in Zr 2 Gibbs free energy of the Fe-based alloy surface as a function of temperature; the Gibbs free energy of the impurity gas with different molecular numbers is used as Zr at a temperature which is more than or equal to 0 2 The antitoxic temperature of the Fe-based alloy.
The invention predicts Zr by theory of first sexual principle 2 The Fe-based alloy has the advantages of resisting the poisoning condition of impurity gas, greatly shortening the time and the raw material cost of experimental test, along with universal applicability and outstanding effect. The invention can avoid or relieve Zr 2 Impurity poisoning problem of Fe-based alloy in hydrogen/deuterium/tritium absorption process, thereby improving Zr 2 Fe-based hydrogen absorption properties.
Drawings
FIG. 1 is a graph showing the Gibbs free energy of carbon monoxide as a function of temperature during adsorption on an alloy surface;
FIG. 2 is Zr 2 XRD pattern of Fe sample;
FIG. 3 is a graph of Zr in the absence and presence of carbon monoxide 2 Hydrogen absorption cycle diagram of Fe alloy at room temperature and 350 ℃.
Detailed Description
The invention provides a method for rapidly determining Zr 2 A method for detoxifying an Fe-based alloy comprising the steps of: calculation of impurity gas in Zr according to density functional theory of first sexual principle 2 The number of saturated adsorption molecules on the surface of the Fe-based alloy;
thermodynamic calculation based on first principle of naturality for adsorbing different molecular numbersImpurity gas in Zr 2 Gibbs free energy of the Fe-based alloy surface as a function of temperature;
the Gibbs free energy of the impurity gas with different molecular numbers is used as Zr at a temperature which is more than or equal to 0 2 The antitoxic temperature of the Fe-based alloy.
Calculation of impurity gas in Zr according to density functional theory of first sexual principle 2 Number of saturated adsorbed molecules on the surface of the Fe-based alloy. In the present invention, the impurity gas preferably includes one or more of carbon monoxide, oxygen and carbon dioxide, more preferably carbon monoxide.
The invention calculates the impurity gas in Zr according to the density functional theory 2 The process of the number of saturated adsorption molecules on the surface of the Fe-based alloy is not particularly required, and the number is calculated by a method known in the art.
In the present invention, the number of molecules of the impurity gas adsorbed is related only to the kind of impurity gas, and is not related to the content of impurity gas. For example: when the impurity gas is carbon monoxide, zr is calculated 2 The Fe-based alloy can adsorb 13 CO molecules at most, namely the number of saturated adsorption molecules for CO is 13.
Obtaining impurity gas in Zr 2 After the saturated adsorption molecular number on the surface of the Fe-based alloy, the invention calculates and adsorbs impurity gases with different molecular numbers on Zr based on the thermodynamics of the first principle 2 The gibbs free energy of the Fe-based alloy surface as a function of temperature.
When the impurity gas is CO, the thermodynamic formula based on the first principle of the invention is shown as formula 1:
in formula 1, the first term is total energy of n CO molecules on the alloy surface calculated by DFT, the second term is total energy of the alloy surface calculated by DFT, the third term is total energy of n CO molecules calculated by DFT, the fourth term is chemical potential of CO molecules at different temperatures including vibration and rotation contribution, and the last term is contribution of temperature and CO partial pressure to CO chemical potential.
The invention takes the temperature which is equal to or more than 0 and corresponds to the Gibbs free energy of the impurity gas with different adsorbed molecular numbers as Zr 2 The antitoxic temperature of the Fe-based alloy.
In the invention, the Gibbs free energy of the impurity gas with different molecular numbers is more than or equal to 0, which represents that the impurity gas is in Zr 2 The surface of the Fe-based alloy is completely desorbed. Namely, the invention takes the temperature at which the impurity gas is completely desorbed as Zr 2 The antitoxic temperature of the Fe-based alloy.
The invention preferably draws impurity gases with different molecular numbers in Zr 2 The Gibbs free energy linear diagram of the surface adsorption process of the Fe-based alloy along with the temperature change can intuitively obtain the desorption temperature of impurity gas.
The invention provides a method for improving Zr 2 A method for detoxifying an Fe-based alloy comprising the steps of:
determination of Zr according to the method described in the above scheme 2 The antitoxic temperature of the Fe-based alloy;
zr is made to be 2 The Fe-based alloy absorbs hydrogen at the antitoxic temperature.
The determination process of the antitoxic temperature is not repeated.
In the present invention, the Zr 2 The Fe-based alloy is provided with Zr 2 Zr of Fe phase crystal structure 2 One or more of Fe-based binary alloy, ternary alloy and quaternary alloy. In the present invention, the Zr 2 The Fe-based ternary alloy may be Zr 2 (Mn 1-x )Fe X 、(Zr x Ti 1-x ) 2 Fe; the Zr is 2 The Fe-based quaternary alloy can be (Zr) 0.5 Ti 0.5 ) 1.05 FeMn. The invention controls Zr 2 The Fe-based alloy is Zr 2 The Fe phase crystal structure has the advantages of high dynamic speed and good cycle stability.
In the present invention, the Zr 2 The particle size of the Fe-based alloy is preferably 70-120 meshes, and the purity is preferably>99%. The invention relates to the Zr 2 The source of the Fe-based alloy is not particularly limited, and commercially available products known in the art may be used. In an embodiment of the present invention, the Zr 2 The Fe-based alloy is produced by Beijing nonferrous metals research institute and prepared by adopting an arc melting method.
In the present invention, the catalyst is preferably used for the reaction of Zr before the hydrogen absorption 2 The Fe-based alloy is activated, preferably at 400 ℃, for a time of preferably 2 hours. The method removes the oxide on the surface by activation, so that Zr 2 The Fe-based alloy has better performance.
In the present invention, the hydrogen-absorbing hydrogen preferably includes hydrogen, deuterium gas or tritium gas, or hydrogen composed of any two isotopes of hydrogen, deuterium, tritium.
In the present invention, the pressure of the hydrogen absorption is preferably 1bar.
The following examples provide a rapid determination of Zr in accordance with the present invention 2 Method for improving poisoning temperature of Fe-based alloy and Zr 2 The method of the anti-poisoning properties of the Fe-based alloy is described in detail, but they should not be construed as limiting the scope of the invention.
Example 1
Based on the first principle of density functional theory, the method calculates the carbon monoxide in Zr 2 Adsorption structure on Fe alloy surface to obtain Zr 2 Fe can only adsorb 13 CO at most, and when adsorbing 8 COs, no adsorption site of hydrogen exists, namely no hydrogen is adsorbed;
and then, according to the thermodynamics of the first principle, the Gibbs free energy of carbon monoxide in the adsorption process of the alloy surface along with the change of temperature is calculated, the result is shown in figure 1, 0CO and 4CO represent the number of CO molecules adsorbed on the alloy surface, and the like. It was found that Zr under room temperature conditions 2 The Fe alloy surface is always saturated with carbon monoxide (FIG. 2 shows Zr at room temperature 2 The Fe alloy still has at least 8 COs on the surface, in this case, zr is considered to be 2 The surface of Fe alloy is saturated and covered by carbon monoxide, and as the temperature increases, the carbon monoxide is immediately used for Zr 2 The Fe alloy surface desorbs, at a temperature of about 350 ℃, carbon monoxide from Zr 2 The surface of Fe alloy is completely desorbed, and the temperature is taken as Zr 2 The temperature at which the Fe alloy resists poisoning.
Verifying the anti-poisoning temperature:
zr prepared by adopting Beijing nonferrous metals research institute production and arc melting method 2 Fe compound as sample with particle size of 70-120 mesh and purity>99％。
FIG. 2 is Zr 2 XRD pattern of Fe sample. It can be seen that sample Zr 2 The Fe compound exhibits a polycrystalline structure, comprising two phases. The main phase corresponds to Zr 2 Fe intermetallic phase, while secondary phase Zr 2 FeO x Is produced by oxidation of metals.
(1) Zr is Zr 2 Activating Fe sample at 400 deg.C for 2 hr, activating Zr 2 The Fe alloy is weighed by 1.5g, and is put into a reaction kettle of a Sievert device to carry out hydrogen absorption performance test in a pure hydrogen atmosphere, the hydrogen absorption pressure is 1bar, the hydrogen absorption temperature is room temperature, the temperature is increased to 350 ℃ after the first time of hydrogen absorption to saturation, vacuumizing and dehydrogenation are carried out for 3h, the temperature is reduced to 25 ℃ to carry out second time of hydrogen absorption, and the total circulation is three times, and the result is shown as a in figure 3.
(2) Hydrogen absorption test in the presence of carbon monoxide with reference to step (1), the gas composition being in particular 95vol.% H 2 +5vol.% CO, the result is shown in fig. 3 b, and since it is substantially free of hydrogen absorption, one test was performed without repeating the second and third times. As can be seen from FIGS. 3 a and b, carbon monoxide severely affects Zr at room temperature 2 The hydrogen absorption performance of the Fe alloy proves the accuracy of the first principle calculation prediction.
The above test was repeated except that the hydrogen absorption temperature was 350℃and the Zr was tested at 350℃in the absence and presence of carbon monoxide 2 The hydrogen absorption performance of the Fe alloy is shown in FIG. 3. In FIG. 3 c and d are Zr in the absence and presence of carbon monoxide, respectively 2 Hydrogen absorption cycle diagram of Fe alloy at 350 ℃. As can be seen from the figure, increasing the temperature significantly eases the carbon monoxide to Zr 2 The poisoning effect of the hydrogen absorption performance of the Fe alloy proves that the accuracy of the first principle calculation prediction of the preferred temperature is high.
Note that: in fig. 3, the abscissas of a and c agree with each other, and the abscissas of b are time (h).
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (6)
1. Zr is confirmed fast 2 A method for the detoxification temperature of an Fe-based alloy, comprising the steps of: calculation of impurity gas in Zr according to density functional theory of first sexual principle 2 The number of saturated adsorption molecules on the surface of the Fe-based alloy; the impurity gas includes one or more of carbon monoxide, oxygen and carbon dioxide; the Zr is 2 The Fe-based alloy is provided with Zr 2 Zr of Fe phase crystal structure 2 One or more of Fe-based binary, ternary and quaternary alloys;
thermodynamic calculation based on first principle to adsorb impurity gas with different molecular numbers in Zr 2 Gibbs free energy of the Fe-based alloy surface as a function of temperature;
the Gibbs free energy of the impurity gas with different molecular numbers is used as Zr at a temperature which is more than or equal to 0 2 The antitoxic temperature of the Fe-based alloy.
2. Zr is improved 2 The method for the anti-poisoning performance of the Fe-based alloy is characterized by comprising the following steps of:
determination of Zr according to the method of claim 1 2 The antitoxic temperature of the Fe-based alloy;
zr is made to be 2 The Fe-based alloy absorbs hydrogen at the antitoxic temperature.
3. The method of claim 2, wherein the hydrogen absorption pressure is 1bar.
4. The method of claim 2, further comprising, prior to the hydrogen absorption, the step of adding to Zr 2 The Fe-based alloy is activated, wherein the activation temperature is 400 ℃ and the activation time is 2h.
5. The method of claim 2, wherein the hydrogen-absorbing gas comprises hydrogen, deuterium, or tritium, or hydrogen comprising any two isotopes of hydrogen, deuterium, or tritium.
6. The method according to claim 2, wherein the Zr is 2 The particle size of the Fe-based alloy is 70-120 meshes, and the purity is high>99％。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4661415A (en) * | 1984-10-27 | 1987-04-28 | Nihon Yakin Kogyo Kabushiki Kaisha | Hydrogen absorbing zirconium alloy |
| US5441715A (en) * | 1991-03-26 | 1995-08-15 | Matsushita Electric Industrial Co., Ltd. | Method for the separation of hydrogen isotopes using a hydrogen absorbing alloy |
| US5669961A (en) * | 1993-07-12 | 1997-09-23 | Lockheed Martin Idaho Technologies Company | Method for the purification of noble gases, nitrogen and hydrogen |
| US6129789A (en) * | 1995-12-21 | 2000-10-10 | Kabushiki Kaisha Toyoda Jidoshokki Seisakusho | Surface treatment method of hydrogen absorbing alloy |
| CN102909030A (en) * | 2012-09-12 | 2013-02-06 | 浙江工业大学 | Ferrous oxide-based ammonia synthesis catalyst |
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| JP5146934B2 (en) * | 2005-08-11 | 2013-02-20 | 株式会社Ｇｓユアサ | Hydrogen storage alloy, hydrogen storage alloy electrode, secondary battery, and method for producing hydrogen storage alloy |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4661415A (en) * | 1984-10-27 | 1987-04-28 | Nihon Yakin Kogyo Kabushiki Kaisha | Hydrogen absorbing zirconium alloy |
| US5441715A (en) * | 1991-03-26 | 1995-08-15 | Matsushita Electric Industrial Co., Ltd. | Method for the separation of hydrogen isotopes using a hydrogen absorbing alloy |
| US5669961A (en) * | 1993-07-12 | 1997-09-23 | Lockheed Martin Idaho Technologies Company | Method for the purification of noble gases, nitrogen and hydrogen |
| US6129789A (en) * | 1995-12-21 | 2000-10-10 | Kabushiki Kaisha Toyoda Jidoshokki Seisakusho | Surface treatment method of hydrogen absorbing alloy |
| CN102909030A (en) * | 2012-09-12 | 2013-02-06 | 浙江工业大学 | Ferrous oxide-based ammonia synthesis catalyst |
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