CN115092889B - Magnesium hydride and preparation method thereof - Google Patents
Magnesium hydride and preparation method thereof Download PDFInfo
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- CN115092889B CN115092889B CN202211028869.8A CN202211028869A CN115092889B CN 115092889 B CN115092889 B CN 115092889B CN 202211028869 A CN202211028869 A CN 202211028869A CN 115092889 B CN115092889 B CN 115092889B
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 229910012375 magnesium hydride Inorganic materials 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 105
- 239000001257 hydrogen Substances 0.000 claims abstract description 103
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 103
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 70
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 8
- 238000011282 treatment Methods 0.000 claims description 45
- 238000000354 decomposition reaction Methods 0.000 claims description 15
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 4
- 238000003801 milling Methods 0.000 claims description 3
- 238000007780 powder milling Methods 0.000 claims description 3
- 238000009689 gas atomisation Methods 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 230000036632 reaction speed Effects 0.000 abstract description 5
- 230000035484 reaction time Effects 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 30
- 239000007789 gas Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000011232 storage material Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 2
- 238000010902 jet-milling Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000007792 addition Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000006467 substitution reaction 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
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/04—Hydrides of alkali metals, alkaline earth metals, beryllium or magnesium; Addition complexes thereof
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Abstract
The invention discloses a magnesium hydride and a preparation method thereof, wherein the magnesium hydride is prepared by repeatedly processing the magnesium metal powder raw material through prehydrogenation and dehydrogenation by controlling the reaction temperature, the reaction pressure and the reaction time, and after repeated times, the surface of the powder is cracked and pulverized due to the large volume change in the hydrogenation and dehydrogenation processes, so that the hydrogenation reaction can be smoothly carried out towards the inside of the particles, the limitation of low reaction speed in the direct hydrogenation method for preparing magnesium hydride by using magnesium metal is broken through, and a magnesium hydride product with high hydrogenation degree and high hydrogen content can be obtained. In addition, the preparation process is simple and low in cost, so that the method for preparing the magnesium hydride is beneficial to industrial production.
Description
Technical Field
The invention relates to the technical field of hydrogen energy, in particular to magnesium hydride and a preparation method thereof.
Background
Nowadays, mankind is faced with energy crisis and environmental pollution are becoming more serious problems, and therefore, development of energy conversion of clean renewable energy instead of fossil energy is urgent. Hydrogen has been widely noticed as a clean and renewable energy source. At present, the bottleneck restricting the wide application of hydrogen energy is mainly how to carry out safe and efficient hydrogen storage and transportation, and the development of the hydrogen storage technology based on solid hydrogen storage materials is praised as an effective method for solving the problem of hydrogen storage. Among the numerous hydrogen storage materials, magnesium hydride (MgH) 2 ) As a solid-state hydrogen storage material, having a theoretical hydrogen content of up to 7.6 wt.%, is a safe way of storing hydrogen as it stores hydrogen in solid-state form in magnesium metal.
The existing method usually adopts a thermal field assisted mechanical ball milling method or directly hydrogenates magnesium metal in a hydrogen atmosphere to prepare magnesium hydride so as to realize hydrogen storage by utilizing the magnesium metal, but because the magnesium hydride is firstly generated on the surface of the magnesium metal, the generated solid magnesium hydride is just like a layer of passive film wrapped outside the magnesium metal to form a core-shell structure (core-metal magnesium, shell-magnesium hydride), which hinders the hydrogenation reaction from smoothly proceeding to the inside of a solid material, so that the hydrogenation degree of a final product is low, the hydrogen content is low, and how to realize the improvement of the hydrogen content of the magnesium hydride becomes a problem to be solved urgently at present.
Disclosure of Invention
The invention provides magnesium hydride and a preparation method thereof, which aim to solve the problem of low hydrogen content of magnesium hydride in the prior art.
In a first aspect, the present invention provides a process for the preparation of magnesium hydride, the process comprising: step one, the metal magnesium powder raw material in a hydrogenation reactor is subjected to a first preset temperature T 1 And a first predetermined hydrogen pressure P H1 Is maintained for a first preset time t 1 Carrying out hydrogenation treatment to obtain a primary magnesium hydride product; step two, raising the temperature in the hydrogenation reactor to a second preset temperature T 2 And maintaining the second preset time t 2 Carrying out dehydrogenation treatment on the primary magnesium hydride product to obtain a magnesium product after dehydrogenation treatment; repeating the first step and the second step for a preset number of times N, and finally, keeping the hydrogen pressure P at a second preset pressure H2 And a first predetermined temperature T 1 Under the condition of keeping for a third preset time t 3 And (4) carrying out hydrogenation treatment on the magnesium product subjected to the repeated hydrogenation and dehydrogenation treatment to prepare the final magnesium hydride product.
Optionally, the first preset hydrogen pressure P H1 Is 0.5MPa to 6MPa, the first preset time t 1 From 1 to 20 hours.
Optionally, the first preset temperature T 1 Comprises the following steps: the first preset hydrogen pressure P H1 Lower corresponding theoretical decomposition temperature T of magnesium hydride theo Minus 10 to 200 ℃.
Optionally, the first preset hydrogen pressure P H2 0.5MPa, corresponding to the theoretical decomposition temperature T of magnesium hydride theo Is 350, then the first preset temperature T 1 The temperature is 340 to 150 ℃;
the first preset hydrogen pressure P H1 0.5MPa, the first preset temperature T 1 340 to 150 ℃;
the first preset hydrogen pressure P H1 1MPa, the first preset temperature T 1 377 ℃ to 187 ℃;
the first preset hydrogen pressure P H1 Is 2MPa, the first preset temperature T 1 417 to 227 ℃;
the first preset hydrogen pressure P H1 Is 3MPa, the first preset temperature T 1 444 to 254 ℃;
the first preset hydrogen pressure P H1 Is 4MPa, the first preset temperature T 1 At 465 to 275 ℃;
the first preset hydrogen pressure P H1 Is 5MPa, the first preset temperature T 1 481 to 291 ℃;
the first preset hydrogen pressure P H1 Is 6MPa, the first preset temperature T 1 The temperature is 496 to 306 ℃.
Optionally, the second preset temperature T 2 Comprises the following steps: the first preset hydrogen pressure P H1 Lower corresponding theoretical decomposition temperature T of magnesium hydride theo Adding 10 to 150 ℃.
Optionally, at the first preset hydrogen pressure P H1 At 0.5MPa, the second preset temperature T 2 The temperature is 360 to 500 ℃; at the first preset hydrogen pressure P H1 At 1MPa, the second preset temperature T 2 397 to 537 ℃; at the first preset hydrogen pressure P H1 At 2MPa, the second preset temperature T 2 437 to 577 ℃; at the first preset hydrogen pressure P H1 At 3MPa, the second preset temperature T 2 464 to 604 ℃; at the first preset hydrogen pressure P H1 At 4MPa, the second preset temperature T 2 485 to 625 ℃; at the first preset hydrogen pressure P H1 At 5MPa, the second preset temperature T 2 The temperature is 501 to 641 ℃; at the first preset hydrogen pressure P H1 At 6MPa, the second preset temperature T 2 The temperature ranges from 516 ℃ to 656 ℃.
Optionally, the second preset time t 2 From 10 minutes to 5 hours; the third preset time t 3 From 1 to 150 hours.
Optionally, the preset number N is 1 to 20.
Optionally, the raw material of the magnesium metal powder is gas atomized powder, milling powder, jet milling powder or ball milling powder, and the powder particle size of the raw material of the magnesium metal powder is between 1 micron and 200 microns.
In a second aspect, the present invention provides a magnesium hydride prepared by any one of the methods described above.
The invention has the following beneficial effects:
the invention carries out repeated treatment of prehydrogenation and dehydrogenation treatment on the magnesium metal powder raw material by controlling the reaction temperature, the reaction pressure and the reaction time, and after repeated treatment for a plurality of times, the surface of the powder is cracked and pulverized due to the large volume change in the hydrogenation and dehydrogenation processes, thereby being beneficial to the smooth proceeding of the hydrogenation reaction to the inside of the particles, breaking through the limitation of slow reaction speed when magnesium hydride is prepared by a direct magnesium metal hydrogenation method, and simultaneously obtaining the magnesium hydride product with high hydrogenation degree and high hydrogen content. In addition, the preparation process is simple and low in cost, so that the method for preparing the magnesium hydride is beneficial to industrial production.
The above description is only an overview of the technical solutions of the present invention, and the present invention can be implemented in accordance with the content of the description so as to make the technical means of the present invention more clearly understood, and the above and other objects, features, and advantages of the present invention will be more clearly understood.
Drawings
Various additional advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
fig. 1 is a schematic flow chart of a method for preparing magnesium hydride according to a first embodiment of the present invention.
Detailed Description
The embodiment of the invention aims at the problems that the reaction for preparing magnesium hydride by directly hydrogenating magnesium metal in a hydrogen atmosphere is a process with slow reaction speed, the hydrogenation degree of the product is low, the hydrogen content is low, very high hydrogen pressure is needed in the reaction process, the reaction time is long and the like, the repeated treatment of pre-hydrogenation and dehydrogenation treatment is carried out on the magnesium metal powder raw material by controlling the reaction temperature, the reaction pressure and the reaction time, and after repeated times, the surface of the powder is cracked and pulverized due to large volume change in the hydrogenation and dehydrogenation processes, so that the hydrogenation reaction can be smoothly carried out towards the inside of particles, the limitation that the reaction speed is slow when the magnesium hydride is prepared by a direct magnesium hydride method is broken through, and magnesium hydride products with high hydrogenation degree and high hydrogen content can be obtained. The present invention will be described in further detail below with reference to the drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
A first embodiment of the present invention provides a method for preparing magnesium hydride, referring to fig. 1, the method comprising:
s101, subjecting a metal magnesium powder raw material in a hydrogenation reactor to a first preset temperature T 1 And a first predetermined hydrogen pressure P H1 Is maintained for a first preset time t 1 Carrying out hydrogenation treatment to obtain a primary magnesium hydride product;
in specific implementation, the embodiment of the present invention may set the first preset hydrogen pressure P H1 0.5MPa to 6MPa, a first preset time t 1 From 1 to 20 hours.
And the first preset temperature T in the embodiment of the invention 1 Comprises the following steps: the first preset hydrogen pressure P H1 Lower theoretical decomposition temperature T of magnesium hydride theo Minus 10 to 200 ℃.
That is, the first embodiment of the present inventionPreset temperature T 1 Is based on a first preset hydrogen pressure P H1 Lower corresponding theoretical decomposition temperature T of magnesium hydride theo May be set, for example, a first preset hydrogen pressure P may be set H2 0.5MPa, corresponding to the theoretical decomposition temperature T of magnesium hydride theo Is 350, the first preset temperature T 1 The temperature is 340 to 150 ℃; first preset hydrogen pressure P H1 Is 1MPa, corresponding to the theoretical decomposition temperature T of magnesium hydride theo Is 387, then the first preset temperature T 1 377 ℃ to 187 ℃; first preset hydrogen pressure P H1 Is 2MPa, corresponding to the theoretical decomposition temperature T of magnesium hydride theo Is 387, then the first preset temperature T 1 417 to 227 ℃; first preset hydrogen pressure P H1 Is 3MPa, corresponding to the theoretical decomposition temperature T of magnesium hydride theo 427, the first preset temperature T 1 At 444 to 254 ℃; first preset hydrogen pressure P H1 Is 4MPa, corresponding to the theoretical decomposition temperature T of magnesium hydride theo Is 454, then the first preset temperature T 1 At 465 to 275 ℃; first preset hydrogen pressure P H1 At 5MPa, corresponding to the theoretical decomposition temperature T of magnesium hydride theo 491, a first preset temperature T 1 481 to 291 ℃; first preset hydrogen pressure P H1 Is 6MPa, corresponding to the theoretical decomposition temperature T of magnesium hydride theo Is 506, the first preset temperature T 1 The temperature is 496 to 306 ℃.
Of course, the above is only an example of the method of the present invention, and in the implementation, the skilled person can set the specific first preset hydrogen pressure P according to the actual needs H1 A first preset time t 1 And a first preset temperature T 1 . The present invention is not particularly limited in this regard.
The final effect of step S101 in the embodiment of the present invention is to pre-hydrogenate the magnesium powder raw material to obtain a primary magnesium hydride product, which is prepared for the next step of dehydrogenation.
It should be noted that the raw material of the magnesium metal powder in the embodiment of the present invention may be gas atomized powder, milling powder, jet milling powder or ball milling powder, and the powder particle size of the raw material of the magnesium metal powder in the embodiment of the present invention is between 1 micron and 200 microns.
S102, raising the temperature in the hydrogenation reactor to a second preset temperature T 2 And maintaining the second preset time t 2 Carrying out dehydrogenation treatment on the primary magnesium hydride product to obtain a magnesium product after dehydrogenation treatment;
that is, in the embodiment of the present invention, the dehydrogenation treatment is performed on the primary magnesium hydride after the hydrogenation treatment in the previous step by controlling the reaction conditions.
Specifically, the second preset temperature T in the embodiment of the present invention 2 Comprises the following steps: the first preset hydrogen pressure P H1 Lower corresponding theoretical decomposition temperature T of magnesium hydride theo Adding 10 to 150 ℃ for a second preset time t 2 From 10 minutes to 5 hours.
Specifically, the hydrogen pressure during the hydrogenation and dehydrogenation processes in the embodiment of the present invention may be set to be the same, that is, the hydrogen pressure may be constant during the whole process of the method of the present invention, but it should be noted that the hydrogen pressure may be influenced to some extent because the temperatures of the hydrogenation and dehydrogenation processes are different, and the influence is negligible. Of course, in the specific implementation, a person skilled in the art may also set the pressure of the hydrogen gas during the hydrogenation process according to actual needs, and may also set the pressure of the hydrogen gas during the dehydrogenation process, which is not specifically limited in the present invention.
For example, when the first preset hydrogen pressure P is H1 At 0.5MPa, the second preset temperature T 2 The temperature is 360 to 500 ℃; at the first preset hydrogen pressure P H1 At 1MPa, the second preset temperature T 2 397 to 537 ℃; at the first preset hydrogen pressure P H1 At 2MPa, the second preset temperature T 2 437 to 577 ℃; at the first preset hydrogen pressure P H1 At 3MPa, the second preset temperature T 2 464 to 604 ℃; at the first preset hydrogen pressure P H1 At 4MPa, the second preset temperature T 2 485 to 625 ℃; at the first preset hydrogen pressure P H1 At 5MPa, the second preset temperature T 2 501 to641 deg.C; at the first preset hydrogen pressure P H1 At 6MPa, the second preset temperature T 2 The temperature is 516 to 656 ℃.
Of course, the above is only an example of the method of the present invention, and in practice, the hydrogen pressure P of the specific dehydrogenation process can be set by those skilled in the art according to actual needs H1 A second preset time t 2 And a second predetermined temperature T 2 . That is, the parameters of each reaction condition can be adjusted by those skilled in the art according to actual needs, and the present invention is not particularly limited thereto.
S103, repeatedly executing the first step and the second step for a preset number of times N, and finally, at a second preset hydrogen pressure P H2 And a first preset temperature T 1 Under the condition of keeping for a third preset time t 3 And (3) carrying out hydrogenation treatment on the magnesium product subjected to the hydrogenation and dehydrogenation treatment for multiple times in a circulating manner to prepare the final magnesium hydride product.
It can be understood that the embodiment of the present invention increases the hydrogenation rate of the final magnesium hydride product by repeating the hydrogenation and dehydrogenation processes several times.
It should be noted that, the skilled person can determine the preset times N for repeatedly performing the first step and the second step and other control parameters for each of the hydrogenation and dehydrogenation according to the hydrogenation rate and the cost of the final magnesium hydride product, for example, the preset times can be set to be 1-20 times, etc.
Generally, the embodiment of the invention controls the reaction temperature, the reaction pressure and the reaction time to repeatedly process the prehydrogenation and the dehydrogenation of the magnesium metal powder raw material, and after repeated times, the surface of the powder is cracked and pulverized due to large volume change in the hydrogenation and dehydrogenation processes, so that the hydrogenation reaction is favorably and smoothly carried out to the inside of particles, the limitation of low reaction speed when magnesium hydride is prepared by a direct magnesium metal hydrogenation method is broken through, and magnesium hydride products with high hydrogenation degree and high hydrogen content can be obtained. In addition, the preparation process is simple and low in cost, so that the method for preparing the magnesium hydride is beneficial to industrial production.
In addition, it should be particularly noted that the condition control parameters of the deoxidation in the subsequent repeated hydrogenation in the embodiment of the present invention may be different from the condition control parameters of the first hydrogenation and deoxidation treatment, that is, the conditions of each hydrogenation and dehydrogenation cycle in the embodiment of the present invention may be different, for example, considering that the powder is more broken after each hydrogenation and deoxidation cycle, the time of hydrogenation and dehydrogenation may be appropriately prolonged to ensure the effective performance of hydrogenation and dehydrogenation, thereby, the fragmentation degree of the powder can be further increased when a new hydrogenation and dehydrogenation cycle is performed, and finally, the hydrogenation rate of the product is further improved. The hydrogenation rate of the product can be increased by increasing the hydrogen pressure and increasing the temperature, which is the same principle as that of extending the hydrogenation and dehydrogenation time.
For a better explanation and description of the method according to the embodiments of the invention, it will be explained below by means of several specific examples:
example 1
The embodiment of the invention provides a preparation method of magnesium hydride, which comprises the following steps:
(1) 100g of vacuum crushed magnesium powder raw material with the grain diameter of 40 microns is placed in a high-pressure hydrogen reactor with the pressure of 3MPa, the temperature is raised to 420 ℃, and the vacuum crushed magnesium powder raw material is kept for 2 hours (t) 1 ) Carrying out pre-hydrogenation treatment;
(2) The temperature is raised to 500 ℃ and held for 1 hour (t) 2 ) Carrying out dehydrogenation treatment;
(3) Repeating the steps (1) - (2) 1 time and 3 times respectively, namely, repeating the steps 1 and 3 times respectively, wherein the preset times N for executing the steps are 1 time and 3 times respectively;
(4) Finally, carrying out hydrogenation treatment for 0.5 to 16 hours (t) under the hydrogen pressure of 3MPa and the temperature of 420 DEG C 3 ) Final magnesium hydride products were prepared N =0 times, 1 times and 3 times, respectively.
In addition, the same magnesium powder raw material is put in a high-pressure hydrogen reactor with the pressure of 3MPa, the temperature is increased to 420 ℃, and the magnesium powder is kept for 0.5 to 16 hours for direct hydrogenation treatment, so that a final product (N = 0) is prepared.Comparing three groups of products at different final hydrotreating time t 3 As shown in Table 1, it is clear that the hydrogen content of the sample corresponding to N =3 is substantially the same under the same control parameters>Sample of N =1>The sample with N =0 shows that the method of repeated hydrogenation-dehydrogenation treatment proposed by the invention is beneficial to increase the hydrogen content of the magnesium hydride product.
TABLE 1 comparison of hydrogen contents of magnesium hydride products after different hydrogenation-dehydrogenation treatments of magnesium powder
Example 2
The embodiment of the invention provides a preparation method of magnesium hydride, which comprises the following steps:
(1) Placing 100g of milled magnesium powder raw material with the grain diameter of 200 microns in a 6MPa high-pressure hydrogen reactor, raising the temperature to 496 ℃, and keeping for 3 hours for pre-hydrogenation treatment;
(2) Raising the temperature to 656 ℃, and keeping for 10 minutes for dehydrogenation treatment;
(3) Repeating the steps (1) to (2) for 10 times;
(4) Finally, hydrogenation treatment is carried out for 100 hours at 490 ℃, and a final magnesium hydride product is prepared.
Example 3
The embodiment of the invention provides a preparation method of magnesium hydride, which comprises the following steps:
(1) 100g of gas atomized magnesium powder raw material with the grain diameter of 1 micron is placed in a high-pressure hydrogen reactor with the pressure of 0.5MPa, the temperature is raised to 150 ℃, and the gas atomized magnesium powder raw material is kept for 5 hours for pre-hydrogenation treatment;
(2) Raising the temperature to 360 ℃, and keeping for 5 hours for dehydrogenation treatment;
(3) Repeating the steps (1) to (2) for 5 times;
(4) And finally, carrying out hydrogenation treatment for 150 hours under the hydrogen pressure of 3MPa and the temperature of 400 ℃ to obtain the final magnesium hydride product.
Example 4
The embodiment of the invention provides a preparation method of magnesium hydride, which comprises the following steps:
(1) Placing 100g of milled magnesium powder raw material with the grain diameter of 50 microns in a 6MPa high-pressure hydrogen reactor, raising the temperature to 480 ℃, and keeping for 1 hour for pre-hydrogenation treatment;
(2) Raising the temperature to 550 ℃, and keeping for 1 hour for dehydrogenation treatment;
(3) Repeating the steps (1) to (2) for 1 time;
(4) And finally, carrying out hydrogenation treatment for 20 hours at the temperature of 480 ℃ to obtain the final magnesium hydride product.
Example 5
The embodiment of the invention provides a preparation method of magnesium hydride, which comprises the following steps:
(1) 100g of gas atomized magnesium powder raw material with the grain diameter of 10 microns is placed in a 2MPa high-pressure hydrogen reactor, the temperature is raised to 400 ℃, and the gas atomized magnesium powder raw material is kept for 1 hour for pre-hydrogenation treatment;
(2) Raising the temperature to 500 ℃, and keeping for 1 hour for dehydrogenation treatment;
(3) Repeating the steps (1) to (2) for 3 times;
(4) And finally, carrying out hydrogenation treatment for 1 hour under the hydrogen pressure of 6MPa and the temperature of 450 ℃ to obtain the final magnesium hydride product.
Example 6
The embodiment of the invention provides a preparation method of magnesium hydride, which comprises the following steps:
(1) Placing 100g of flake cut magnesium powder raw material with the grain diameter of 40 microns in a high-pressure hydrogen reactor with the pressure of 3MPa, raising the temperature to 400 ℃, and keeping for 2 hours for pre-hydrogenation treatment;
(2) Raising the temperature to 500 ℃, and keeping for 1 hour for dehydrogenation treatment;
(3) Repeating the steps (1) to (2) for 3 times;
(4) And finally, carrying out hydrogenation treatment for 40 hours at the hydrogen pressure of 3MPa and the temperature of 400 ℃ to obtain the final magnesium hydride product.
Tests show that the magnesium hydride product with higher hydrogenation rate can be quickly obtained by circularly carrying out hydrogenation and dehydrogenation treatment for multiple times, and in addition, the embodiment of the invention can finally and effectively improve the hydrogenation rate of the product by increasing the hydrogenation temperature and prolonging the hydrogenation and dehydrogenation time.
In a second embodiment, the present invention provides a magnesium hydride prepared by the method of any one of the first embodiments of the present invention. The details of which can be understood with reference to the first embodiment of the present invention will not be discussed in detail herein.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, and that the scope of the present invention is not limited to the embodiments disclosed.
Claims (6)
1. A method for preparing magnesium hydride, which is characterized by comprising the following steps:
step one, the metal magnesium powder raw material in a hydrogenation reactor is subjected to a first preset temperature T 1 And a first predetermined hydrogen pressure P H1 Is maintained for a first predetermined time t 1 Carrying out hydrogenation treatment to obtain a primary magnesium hydride product;
step two, raising the temperature in the hydrogenation reactor to a second preset temperature T 2 And maintaining the second preset time t 2 Carrying out dehydrogenation treatment on the primary magnesium hydride product to obtain a magnesium product after dehydrogenation treatment;
repeating the first step and the second step for a preset number of times N, and finally, keeping the hydrogen pressure P at a second preset pressure H2 And a first predetermined temperature T 1 Under the condition of keeping for a third preset time t 3 Carrying out hydrogenation treatment on the magnesium product subjected to the repeated hydrogenation and dehydrogenation treatment to prepare a final magnesium hydride product;
the first preset hydrogen pressure P H1 Is 0.5MPa to 6MPa, and the first preset time t 1 For 1 to 20 hours;
the first preset temperature T 1 Comprises the following steps: the first preset hydrogen pressure P H1 Lower corresponding theoretical decomposition temperature T of magnesium hydride theo Subtracting 10 to 200 ℃;
the second preset temperature T 2 Comprises the following steps: the first preset hydrogen pressure P H1 Lower theoretical decomposition temperature T of magnesium hydride theo Adding 10 to 150 ℃;
the second preset time t 2 From 10 minutes to 5 hours;
the third preset time t 3 From 1 to 150 hours.
2. The method of claim 1,
the first preset hydrogen pressure P H1 0.5MPa, the first preset temperature T 1 The temperature is 340 to 150 ℃; or,
the first preset hydrogen pressure P H1 1MPa, the first preset temperature T 1 377 ℃ to 187 ℃; or,
the first preset hydrogen pressure P H1 Is 2MPa, the first preset temperature T 1 417 to 227 ℃; or,
the first preset hydrogen pressure P H1 Is 3MPa, the first preset temperature T 1 444 to 254 ℃; or,
the first preset hydrogen pressure P H1 Is 4MPa, the first preset temperature T 1 At a temperature of 465 to 275 ℃; or,
the first preset hydrogen pressure P H1 Is 5MPa, the first preset temperature T 1 481 to 291 ℃; or
The first preset hydrogen pressure P H1 Is 6MPa, the first preset temperature T 1 The temperature is 496 to 306 ℃.
3. The method of claim 1,
at the first preset hydrogen pressure P H1 0.5MPa, the second preset temperature T 2 The temperature is 360 to 500 ℃; or,
at the first preset hydrogen pressure P H1 1MPa, the second preset temperature T 2 397 to 537 ℃; or,
at the first preset hydrogen pressure P H1 Is 2MPa, the second preset temperature T 2 437 to 577 ℃; or,
at the first preset hydrogen pressure P H1 Is 3MPa, the second preset temperature T 2 464 to 604 ℃; or,
at the first preset hydrogen pressure P H1 Is 4MPa, the second preset temperature T 2 485 to 625 ℃; or,
at the first preset hydrogen pressure P H1 Is 5MPa, the second preset temperature T 2 The temperature is 501 to 641 ℃; or,
at the first preset hydrogen pressure P H1 Is 6MPa, the second preset temperature T 2 The temperature is 516 to 656 ℃.
4. The method according to any one of claims 1 to 3,
the preset number of times N is 1 to 20.
5. The method according to any one of claims 1 to 3,
the metal magnesium powder raw material is gas atomization powder, milling powder, air current grinding powder or ball milling powder particles, and the particle size of the metal magnesium powder raw material is between 1 micron and 200 microns.
6. Magnesium hydride, characterized in that it is obtained by a process according to any one of claims 1 to 5.
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| CN202211028869.8A Active CN115092889B (en) | 2022-08-26 | 2022-08-26 | Magnesium hydride and preparation method thereof |
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| US4554153A (en) * | 1978-02-02 | 1985-11-19 | Studiengesellschaft Kohle Mbh | Process for the production of magnesium hydrides |
| US5162108A (en) * | 1982-12-22 | 1992-11-10 | Studiengesellschaft Kohle Gmbh | Method of preparing active magnesium-hydride or magnesium hydrogen-storer systems |
| US5199972A (en) * | 1982-12-22 | 1993-04-06 | Studiengesellschaft Kohle G.M.B.H. | Method of preparing active magnesium-hydride or magnesium hydrogen-storer systems |
| CN112723310A (en) * | 2020-12-30 | 2021-04-30 | 榆林学院 | Preparation method of magnesium hydride |
| CN113620246A (en) * | 2021-09-23 | 2021-11-09 | 上海氢投捷能科技有限公司 | Method for preparing granular magnesium hydride |
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| US4554153A (en) * | 1978-02-02 | 1985-11-19 | Studiengesellschaft Kohle Mbh | Process for the production of magnesium hydrides |
| US5162108A (en) * | 1982-12-22 | 1992-11-10 | Studiengesellschaft Kohle Gmbh | Method of preparing active magnesium-hydride or magnesium hydrogen-storer systems |
| US5199972A (en) * | 1982-12-22 | 1993-04-06 | Studiengesellschaft Kohle G.M.B.H. | Method of preparing active magnesium-hydride or magnesium hydrogen-storer systems |
| CN112723310A (en) * | 2020-12-30 | 2021-04-30 | 榆林学院 | Preparation method of magnesium hydride |
| CN113620246A (en) * | 2021-09-23 | 2021-11-09 | 上海氢投捷能科技有限公司 | Method for preparing granular magnesium hydride |
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