A material for decomposing hydrogen isotope water vapor, a preparation method thereof, and a usage method thereof

Abstract

The present invention belongs to the technical field of alloys, and specifically relates to a material for decomposing hydrogen isotope water vapor, a preparation method thereof, and a usage method thereof. The chemical formula of the hydrogen isotope water vapor decomposition material is: Zr1-xTixMn2+y, where 0.7 ≤ x ≤ 0.9 and 0 ≤ y ≤ 0.5. Compared with the prior art, the present invention has at least the following beneficial effects: 1) The hydrogen isotope water vapor decomposition material prepared by the present invention has the advantages of low cost and no radioactivity, and can greatly improve the disadvantages of high cost and certain radioactivity of traditional depleted uranium materials. 2) The hydrogen isotope water vapor decomposition material of the present invention has the advantage of low hydrogen storage capacity at room temperature, and can greatly reduce the retention of hydrogen isotopes during use. 3) The hydrogen isotope water vapor decomposition material of the present invention has the advantage of low use temperature, which is beneficial to reducing the permeation loss of hydrogen isotopes during the water vapor decomposition process.

Description

Technical Field

[0001] The present invention belongs to the technical field of alloys, and particularly relates to a material for hydrogen isotope water vapor decomposition, a preparation method thereof, and a usage method thereof. Background Art

[0002] In the process of hydrogen isotope water vapor decomposition, depleted uranium (U) is usually used as the material for water vapor decomposition, and this material has the advantage of a high water vapor decomposition rate. However, this material also has some disadvantages: First, depleted uranium is a material with strong hydrogen absorption characteristics, and its equilibrium hydrogen pressure at room temperature is about 10 -4 Pa. Once the operation is improper, it is extremely easy to cause the retention loss of hydrogen isotopes; second, the temperature required for water vapor decomposition is relatively high, about 600 - 700 °C, which is likely to cause the permeation loss of hydrogen isotopes; finally, the depleted uranium material is radioactive and has a relatively high usage cost.

[0003] In summary, there is an urgent need to develop a new type of hydrogen isotope water vapor decomposition material with high water vapor decomposition efficiency, high equilibrium hydrogen pressure, and low usage temperature. Summary of the Invention

[0004] The purpose of the present invention is to design a hydrogen isotope water vapor decomposition material with excellent performance to achieve the efficient decomposition of hydrogen isotope water vapor. At the same time, this material can minimize the retention and permeation of hydrogen isotope gas during the decomposition process and significantly reduce energy consumption.

[0005] To this end, in the first aspect of the present invention, there is provided a material for hydrogen isotope water vapor decomposition, and the chemical formula of the water vapor decomposition material is: Zr 1-x Ti x Mn 2+y , where 0.7 ≤ x ≤ 0.9 and 0 ≤ y ≤ 0.5. The numerical changes of 1 - x, x, and 2 + y represent the atomic content ratios among the three elements of Zr, Ti, and Mn.

[0006] Zr has an extremely strong ability to absorb hydrogen isotope gas; the ability of Ti to absorb hydrogen isotope gas is weaker than that of Zr. Increasing the content of Ti can significantly increase the equilibrium hydrogen isotope pressure of the alloy, thereby greatly reducing the amount of hydrogen isotope retention during the decomposition process; the ability of Mn to absorb hydrogen isotope is relatively weak. Increasing the content of Mn is beneficial to increasing the equilibrium hydrogen isotope pressure. However, if the content of Mn is increased too much, a heterogeneous phase will be generated, which is not conducive to the increase of the equilibrium hydrogen isotope pressure of the alloy.

[0007] The inventors of this case have conducted a large number of experimental attempts and found that when Zr 1-x Ti x Mn 2+y, wherein, when 0.7≤x≤0.9 and 0≤y≤0.5, the material for hydrogen isotope water vapor decomposition has the characteristics of high hydrogen isotope absorption platform pressure, high water vapor decomposition efficiency, low operating temperature, low hydrogen isotope penetration and low cost.

[0008] In order to further improve the decomposition efficiency of hydrogen isotope water vapor, as a preferred solution, 0.75≤x≤0.85, 0.2≤y≤0.3, such as Zr 0.2 Ti 0.8 Mn 2.25 .

[0009] As a preferred embodiment, the hydrogen isotope vapor includes HZO and / or Z2O, where Z is protium (H), deuterium (D), or tritium (T). For example, the hydrogen isotope vapor can be H2O, HDO, HTO, D2O, T2O, or a mixture of HDO and T2O.

[0010] The decomposition principles of the above-mentioned materials for hydrogen isotope water vapor decomposition include:

[0011]

[0012] or

[0013]

[0014] Wherein, M is the above-mentioned Zr 1-x Ti x Mn 2+y , 0.7≤x≤0.9, 0≤y≤0.5; HZO and Z2O are hydrogen isotope water vapor, HZ and Z2 are hydrogen isotope gases.

[0015] A second aspect of the present invention provides a method for preparing a material for hydrogen isotope water vapor decomposition, the method comprising:

[0016] Step 1: Zr, Ti, and Mn raw materials are mixed and induction smelted under a first inert gas atmosphere to obtain a first alloy ingot;

[0017] Step 2: heat treating the first alloy ingot under a second inert gas atmosphere to obtain a second alloy ingot;

[0018] Step 3: The second alloy ingot is prepared into alloy powder and / or alloy particles under the protection of a third inert gas to obtain a material for hydrogen isotope water vapor decomposition.

[0019] As a preferred embodiment, the preparation method of the material for hydrogen isotope water vapor decomposition satisfies at least one of the following conditions:

[0020] The impurity content of carbon in the Zr raw material is ≤50 ppm, the impurity content of sulfur is ≤50 ppm, and the impurity content of nitrogen is ≤50 ppm;

[0021] The impurity content of carbon in the Ti raw material is ≤50 ppm, the impurity content of sulfur is ≤50 ppm, and the impurity content of nitrogen is ≤50 ppm;

[0022] The impurity content of carbon in the Mn raw material is ≤50 ppm, the impurity content of sulfur is ≤50 ppm, and the impurity content of nitrogen is ≤50 ppm.

[0023] The requirements for the impurity content of carbon, sulfur, and nitrogen in the above raw materials can ensure that the impurity content of carbon, sulfur, and nitrogen in the prepared hydrogen isotope water vapor decomposition material is lower than ≤50 ppm, preventing the generation of impurity gases such as methane, hydrogen sulfide, and ammonia during the hydrogen isotope water vapor decomposition process. As a further preferred option, the impurity content of carbon, sulfur, and nitrogen in the raw materials should be lower than ≤10 ppm.

[0024] In the above method for preparing the material for hydrogen isotope water vapor decomposition, before step 1, according to the chemical formula Zr 1-x Ti x Mn 2+y calculate the dosage of the raw material, where 0.7 ≤ x ≤ 0.9, 0 ≤ y ≤ 0.5; for Mn, the added burn loss is 0.5 - 3% of the calculated amount.

[0025] In the above method for preparing the material for hydrogen isotope water vapor decomposition, as a preferred option, step 1 satisfies at least one of the following conditions:

[0026] In step 1, put the Zr, Ti, and Mn raw materials into a water-cooled copper crucible for induction melting;

[0027] In step 1, the first inert gas is high-purity argon or high-purity helium.

[0028] Using a water-cooled copper crucible can ensure that the crucible material will not be mixed into the prepared alloy, so that the chemical composition and impurity content of the material for hydrogen isotope water vapor decomposition are not affected.

[0029] Using the induction melting method can control the uniform heating of the material for hydrogen isotope water vapor decomposition during the melting process and reduce the volatilization of Mn caused by excessive local temperature.

[0030] During the melting process, a helium protection atmosphere is used. The helium protection atmosphere can suppress the volatilization of Mn during the melting process to the greatest extent.

[0031] In the above method for preparing the material for hydrogen isotope water vapor decomposition, as a preferred option, step 2 satisfies at least one of the following conditions:

[0032] In Step 2, the second inert gas is high-purity argon or high-purity helium;

[0033] In Step 2, the heat treatment temperature is 900 - 1100 °C;

[0034] In Step 2, the heat treatment holding time is 5 - 20 h.

[0035] Under the temperature condition of 900 - 1100 °C, the alloy has a more stable crystal structure and a more uniform chemical composition.

[0036] In the above preparation method of the material for hydrogen isotope water vapor decomposition, as a preferred scheme, Step 3 satisfies at least one of the following conditions:

[0037] In Step 3, the particle size of the hydrogen isotope water vapor decomposition material is 0.05 - 5 mm;

[0038] In Step 3, the third inert gas is high-purity argon or high-purity helium.

[0039] Among them, the material for hydrogen isotope water vapor decomposition can be made into alloy particles with a particle size of 0.5 - 5 mm by mechanical crushing method.

[0040] The third aspect of the present invention provides a method for using a material for hydrogen isotope water vapor decomposition, including: loading the hydrogen isotope water vapor material onto a foam metal, loading it into a flow-through decomposition bed, heating the flow-through decomposition bed, and turning on the gas circulation device to make the material for hydrogen isotope water vapor decomposition contact with the water vapor to be treated, and completing the decomposition of the water vapor to be treated.

[0041] The above method for using the material for hydrogen isotope water vapor decomposition satisfies at least one of the following conditions:

[0042] The foam metal is selected from at least one of foam copper metal, foam nickel metal, and foam cobalt metal;

[0043] The temperature for heating the decomposition bed is 350 - 600 °C.

[0044] According to the present invention, in a specific embodiment, the method for using the material for hydrogen isotope water vapor decomposition is as follows:

[0045] A. The material for hydrogen isotope water vapor decomposition is used in Figure 1 the system shown, and this system is composed of components such as a flow-through decomposition bed 1, a gas pipeline 2, an outlet valve 3, a gas circulation device 4, an inlet valve 5, a material 6 for hydrogen isotope water vapor decomposition, a foam metal 7, a heating furnace 8, etc.

[0046] B. Load the material 6 for hydrogen isotope water vapor decomposition into the porous metal foam 7 (pore size 0.5 - 5 mm), and then load them together into the flow-through decomposition bed 1.

[0047] C. Connect the inlet and outlet gas pipelines at both ends of the flow-through decomposition bed 1, and control the flow and stillness of the gas through the outlet valve 3 and the inlet valve 5.

[0048] D. The gas circulation device 4 forms a gas circuit circulation with the flow-through decomposition bed 1 through pipelines.

[0049] E. The heating furnace 8 is installed outside the flow-through decomposition bed 1, and the flow-through decomposition bed 1 is heated by resistance heating. The operating temperature of the flow-through decomposition bed 1 is 350 - 600 °C.

[0050] F. The hydrogen isotope water vapor flows through the flow-through decomposition bed 1 and decomposes into hydrogen isotope gas.

[0051] Compared with the prior art, the present invention has at least the following beneficial effects:

[0052] 1) The material for hydrogen isotope water vapor decomposition prepared by the present invention has the advantages of low cost and no radioactivity, and can greatly improve the disadvantages of high cost and certain radioactivity of traditional depleted uranium materials.

[0053] 2) The material for hydrogen isotope water vapor decomposition prepared by the present invention has a high hydrogen absorption platform pressure at room temperature, and can greatly reduce the retention of hydrogen isotopes during use.

[0054] 3) The material for hydrogen isotope water vapor decomposition prepared by the present invention has a relatively low operating temperature, which can reduce the permeation of hydrogen isotopes during the water vapor decomposition process. Description of the Drawings

[0055] Figure 1 Shows a schematic diagram of a usage mode of the material for hydrogen isotope water vapor decomposition of the present invention;

[0056] Figure 2 Shows the water vapor decomposition efficiency of multiple materials for hydrogen isotope water vapor decomposition at 450 °C.

[0057] Explanation of the Reference Numerals in the Drawings

[0058] 1 - Flow-through decomposition bed, 2 - Gas pipeline, 3 - Outlet valve, 4 - Gas circulation device, 5 - Inlet valve, 6 - Material for hydrogen isotope water vapor decomposition, 7 - Porous metal foam, 8 - Heating furnace. Detailed Embodiments

[0059] In the following description, numerous specific details are given to provide a more thorough understanding of the technical solutions provided by the present invention. However, it is obvious to those skilled in the art that the technical solutions provided by the present invention can be implemented without one or more of these details.

[0060] In the examples and comparative examples of the present invention, the Zr raw material is sourced from Beijing Zhongjinyan New Materials Technology Co., Ltd., the Ti raw material is sourced from Beijing Zhongjinyan New Materials Technology Co., Ltd., and the Mn raw material is sourced from Beijing Zhongjinyan New Materials Technology Co., Ltd. Among them, the impurity content of carbon in the Zr raw material is ≤10 ppm, the impurity content of sulfur is ≤50 ppm, and the impurity content of nitrogen is ≤50 ppm; the impurity content of carbon in the Ti raw material is ≤10 ppm, the impurity content of sulfur is ≤50 ppm, and the impurity content of nitrogen is ≤50 ppm; the impurity content of carbon in the Mn raw material is ≤10 ppm, the impurity content of sulfur is ≤50 ppm, and the impurity content of nitrogen is ≤50 ppm.

[0061] Example 1

[0062] This example provides a material for hydrogen isotope water vapor decomposition, its preparation method and usage method. The implementation method is as follows:

[0063] 1) Design the material composition according to the chemical formula of Zr 1-x Ti x Mn 2+y The designed alloy composition chemical formula is: Zr 0.1 Ti 0.9 Mn 2.25

[0064] 2) Calculate the weight of the raw materials of each alloy according to the corresponding chemical formula, and the burn loss of Mn added is 2% of the calculated amount.

[0065] 3) Put the weighed Zr, Ti and Mn raw materials into a water-cooled copper crucible, and then carry out induction melting under a helium atmosphere to obtain an alloy ingot.

[0066] 4) Put the alloy ingot obtained by melting into a tubular heat treatment furnace, and under a helium protection atmosphere, keep it at 1000 °C for 10 hours.

[0067] 5) Under argon protection, make the heat-treated alloy into powder with a particle size range of 0.05 - 5 mm.

[0068] 6) Test the stoichiometric ratio of each element of the heat-treated alloy by inductively coupled plasma mass spectrometry (ICP-MS) to determine its composition.

[0069] 7) At 25 °C, use a fully automatic Sieverts device to test Zr1-x Ti x Mn 2+y Hydrogen absorption performance of the alloy.

[0070] 8) Load the alloy powder onto the copper foam metal with a pore size of 0.5 - 5 mm, and then place it into Figure 1 the flow-through decomposition bed 1 as shown.

[0071] 9) Turn on the heating furnace 8 and use the heating furnace 8 to heat the flow-through decomposition bed 1 to 450 °C.

[0072] 10) Open the outlet valve 3 and the inlet valve 5, turn on the gas circulation device 4, and make the mixed gas flow of hydrogen isotope water vapor and high-purity helium gas flow through the flow-through decomposition bed 1. The hydrogen isotope water vapor is deuterium oxide (D2O) water vapor with a content of 6000 ppm; at the same time, it reacts with the material 6 for the decomposition of hydrogen isotope water vapor, and then decomposes the hydrogen isotope water vapor into hydrogen isotope gas.

[0073] 11) Detect the water vapor content after the decomposition of hydrogen isotope water vapor through a dew point meter, and calculate the decomposition efficiency of the alloy according to the following formula. Among them, : Decomposition efficiency; H 初 : Initial content of hydrogen isotope water vapor; H 终 : Final content of hydrogen isotope water vapor.

[0074]

[0075] Example 2

[0076] This example provides a material for the decomposition of hydrogen isotope water vapor, its preparation method and usage method. Except for changing the alloy composition designed in step 1) to Zr 0.2 Ti 0.8 Mn 2.25 , other conditions are the same as those in Example 1.

[0077] Example 3

[0078] This example provides a material for the decomposition of hydrogen isotope water vapor, its preparation method and usage method. Except for changing the alloy composition designed in step 1) to Zr 0.3 Ti 0.7 Mn 2.25 , other conditions are the same as those in Example 1.

[0079] Example 4

[0080] This example provides a material for the decomposition of hydrogen isotope water vapor, its preparation method and usage method. Except for changing the alloy composition designed in step 1) to Zr 0.2 Ti 0.8Mn 2.0 , the other conditions are the same as those in Example 1.

[0081] Example 5

[0082] This example provides a material for hydrogen isotope water vapor decomposition, its preparation method and usage method. Except that the alloy composition designed in step 1) is changed to Zr 0.2 Ti 0.8 Mn 2.5 , the other conditions are the same as those in Example 1.

[0083] Comparative Example 1

[0084] The difference from Example 1 is only that the designed alloy is changed to Zr 0.4 Ti 0.6 Mn 2.25 , the other conditions are the same as those in Example 1.

[0085] Comparative Example 2

[0086] The difference from Example 1 is only that the designed alloy is changed to Zr 0.2 Ti 0.8 Mn 1.9 , the other conditions are the same as those in Example 1.

[0087] Comparative Example 3

[0088] The difference from Example 1 is only that the designed alloy is changed to Zr 0.2 Ti 0.8 Mn 2.6 , the other conditions are the same as those in Example 1.

[0089] The stoichiometric ratios of all elements of the heat-treated alloys were tested by inductively coupled plasma mass spectrometry (ICP-MS), and the test results are shown in Table 1.

[0090] Table 1 Elemental composition of Zr 1-x Ti x Mn 2+y alloy

[0091]

[0092] The above results show that the chemical element compositions and the ratios of each element of the prepared alloys in the examples and comparative examples are basically consistent with the designed alloys.

[0093] The hydrogen absorption performance of all alloys was tested by a fully automatic Sieverts device, and the test results are shown in Table 2.

[0094] Table 2 Elemental composition of Zr 1-x Ti x Mn2+y Hydrogen Absorption Performance of the Alloy

[0095]

[0096] The above results show that the hydrogen storage capacities of the alloys in Examples 1-5 and the alloys in Comparative Examples 1-3 are relatively low, and the hydrogen absorption plateau pressures are relatively high, which is beneficial to the retention of hydrogen isotope gases during the hydrogen isotope water vapor decomposition process. In addition, when the Mn ratio is constant, the hydrogen storage capacity increases and the hydrogen absorption plateau pressure gradually decreases as the Zr ratio increases; when the Zr:Ti ratio is constant, the hydrogen storage capacity decreases and the hydrogen absorption plateau pressure increases as the Mn ratio increases.

[0097] The water vapor content after the decomposition of hydrogen isotope water vapor was detected by a dew point meter, and the results are as Figure 2 shown. It can be clearly found that the hydrogen isotope water vapor decomposition efficiencies of the alloys in Examples 1-5 are all ≥99.51%, and the hydrogen isotope water vapor decomposition efficiencies of the alloys in Comparative Examples 1-3 are all ≤98.84%. In the decomposition operation of hydrogen isotope water vapor, the water vapor decomposition efficiency should be above 99.5%. Therefore, for the Zr 1-x Ti x Mn 2+y alloy, the value range of x should be 0.7 ≤ x ≤ 0.9, and the value range of y should be 0 ≤ y ≤ 0.5.

[0098] The above are only the preferred embodiments of the present invention and are not used to limit the present invention. For those skilled in the art, the present invention can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A material for the decomposition of hydrogen isotope water vapor, characterized in that, The chemical formula of the material for hydrogen isotope water vapor decomposition is: Zr 1-x Ti x Mn 2+y , where 0.7 ≤ x ≤ 0.9 and 0 ≤ y ≤ 0.

5.

2. The material for hydrogen isotope water vapor decomposition according to claim 1, wherein The hydrogen isotope water vapor includes HZO and / or Z2O; Z is protium, deuterium or tritium.

3. The preparation method of the material for hydrogen isotope water vapor decomposition according to claim 1, characterized in that, The preparation method includes: Step 1: Mix the Zr, Ti and Mn raw materials, and perform induction melting in a first inert gas atmosphere to obtain a first alloy ingot; Step 2: Perform heat treatment on the first alloy ingot under the protection of a second inert gas atmosphere to obtain a second alloy ingot; Step 3: Make the second alloy ingot into alloy powder or alloy particles under the protection of a third inert gas to obtain a material for decomposing hydrogen isotope water vapor.

4. The preparation method of the material for decomposing hydrogen isotope water vapor according to claim 3, characterized in that: The impurity content of carbon in the Zr raw material is ≤50 ppm, the impurity content of sulfur is ≤50 ppm, and the impurity content of nitrogen is ≤50 ppm; The impurity content of carbon in the Ti raw material is ≤50 ppm, the impurity content of sulfur is ≤50 ppm, and the impurity content of nitrogen is ≤50 ppm; The impurity content of carbon in the Mn raw material is ≤50 ppm, the impurity content of sulfur is ≤50 ppm, and the impurity content of nitrogen is ≤50 ppm.

5. The preparation method of the material for hydrogen isotope water vapor decomposition according to claim 3, characterized in that, Before performing Step 1, calculate the amount of raw materials according to the chemical formula Zr 1-x Ti x Mn 2+y where 0.7 ≤ x ≤ 0.9 and 0 ≤ y ≤ 0.5; Among them, the burning loss of the added Mn is 0.5-3% of the calculated amount.

6. The preparation method of the material for decomposing hydrogen isotope water vapor according to claim 3, characterized in that: In step 1, the Zr, Ti and Mn raw materials are put into a water-cooled copper crucible for induction melting; In step 1, the first inert gas is high-purity argon or high-purity helium.

7. The preparation method of the material for decomposing hydrogen isotope water vapor according to claim 3, characterized in that: In step 2, the second inert gas is high-purity argon or high-purity helium; In step 2, the heat treatment temperature is 900-1100 °C; In step 2, the heat treatment holding time is 5-20 h.

8. The preparation method of the material for decomposing hydrogen isotope water vapor according to claim 3, characterized in that: In step 3, the particle size of the hydrogen isotope water vapor decomposition material is 0.05-5 mm; In step 3, the third inert gas is high-purity argon or high-purity helium.

9. The method of using the material for hydrogen isotope water vapor decomposition according to claim 1, characterized in that, It includes: Load the hydrogen isotope water vapor decomposition material on the foam metal, put it into a flow-through decomposition bed, heat the flow-through decomposition bed, and turn on the gas circulation device to make the material for decomposing hydrogen isotope water vapor contact with the water vapor to be treated, and complete the decomposition of the water vapor to be treated.

10. The usage method of the material for decomposing hydrogen isotope water vapor according to claim 9, characterized in that: The foam metal is selected from at least one of foam copper metal, foam nickel metal and foam cobalt metal; The temperature for heating the decomposition bed is 350-600 °C.

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