CN114160784B - Nd-containing material4Mg80Ni8Composite material for preparing hydrogen by hydrolyzing alloy and pure Mg, preparation method and application thereof - Google Patents
Nd-containing material4Mg80Ni8Composite material for preparing hydrogen by hydrolyzing alloy and pure Mg, preparation method and application thereof Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 96
- 239000001257 hydrogen Substances 0.000 title claims abstract description 96
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 92
- 239000000956 alloy Substances 0.000 title claims abstract description 92
- 230000003301 hydrolyzing effect Effects 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 73
- 239000002131 composite material Substances 0.000 claims abstract description 63
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 52
- 230000007062 hydrolysis Effects 0.000 claims abstract description 47
- 239000000843 powder Substances 0.000 claims abstract description 36
- 238000000498 ball milling Methods 0.000 claims abstract description 21
- 230000007797 corrosion Effects 0.000 claims abstract description 13
- 238000005260 corrosion Methods 0.000 claims abstract description 13
- 238000003723 Smelting Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000011812 mixed powder Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 238000004381 surface treatment Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000007547 defect Effects 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 230000006698 induction Effects 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 abstract description 156
- 230000000694 effects Effects 0.000 abstract description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000036632 reaction speed Effects 0.000 abstract 1
- 238000007711 solidification Methods 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000013535 sea water Substances 0.000 description 5
- 238000005266 casting Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910019086 Mg-Cu Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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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
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/08—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents with metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Engineering & Computer Science (AREA)
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- Combustion & Propulsion (AREA)
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Abstract
The invention discloses a hydrolytic hydrogen production composite material containing Nd 4Mg80Ni8 alloy and pure Mg, a preparation method and application thereof, wherein the mass percentage of Mg element in the hydrolytic hydrogen production composite material is 65-90% of that of the composite material. The invention adopts Mg block, nd block and Ni block raw materials, mixes the raw materials according to proportion, then carries out smelting and solidification to obtain Nd 4Mg80Ni8 alloy, then mixes the Nd 4Mg80Ni8 alloy with Mg powder, carries out ball milling on the mixed powder to obtain the hydrolysis hydrogen production composite material containing Nd 4Mg80Ni8 alloy and pure Mg. According to the invention, by adjusting the component proportion of Nd 4Mg80Ni8 alloy and pure Mg, the alloy galvanic corrosion effect is introduced to improve the yield and the speed of hydrogen production by hydrolysis, and meanwhile, the reaction speed and the yield of the magnesium-based hydrogen production material by hydrolysis are greatly improved, and the composite material has the advantages of simple preparation process, low production cost and convenience for industrial production.
Description
Technical Field
The invention provides a hydrolysis hydrogen production composite material, a preparation method and application thereof, and belongs to the technical field of hydrogen production.
Background
The energy is an important material foundation for supporting the current civilization and social development of human beings, and is indispensible from the production and life of human beings. With the rapid development of society, the population is continuously increased, and the demand and consumption of energy by human are also continuously increased, which causes great damage to the environment. Thus, there is an ongoing effort to find a new and environmentally friendly, renewable, clean energy source. Under the promotion of the policy of carbon neutralization, hydrogen can gradually go on an energy stage, and is considered as clean energy capable of replacing fossil fuel due to the advantages of high energy density, abundant reserves, low price, no pollution of combustion byproducts to the environment and the like.
However, about 95% of the commercial hydrogen is still obtained by partial oxidation of natural gas and gasification of coal. Although these hydrogen production technologies are more mature and lower in cost, people's reliance on fossil fuels continues to increase year by year as the demand for hydrogen energy increases. In recent years, under the background of 'carbon peak' and 'carbon neutralization', developing a high-efficiency, safe, environment-friendly and low-cost hydrogen production technology becomes a great importance in preparing 'green hydrogen'.
The reaction condition of hydrogen production by adopting Mg hydrolysis is mild, expensive catalysts are not needed, the method can be realized in a standard atmospheric environment, and the Mg has the advantages of rich resources, low price, low density and the like, so that the method is more and more widely paid attention to people. If the weight of water is not taken into account, hydrolysis of Mg may result in an ultra-high hydrogen capacity of 8.2 wt.%. Therefore, the hydrolysis reaction of Mg to produce hydrogen is considered as a promising method for replacing fossil fuel to produce hydrogen. However, a large amount of Mg (OH) 2 passivation layer is generated during Mg hydrolysis and covers the surface of the reactant, so that the reaction is hindered, the hydrogen production reaction is difficult to complete, and the kinetics of the hydrogen production is slow. Researches show that the magnesium alloy prepared by adding transition metal elements or rare earth metal elements into Mg can effectively solve the problem, the second phase of the magnesium alloy and the Mg phase generate galvanic corrosion effect, the corrosion rate (Oh S K,Kim H W,Kim M J,et al.Design of Mg-Cu alloys for fast hydrogen production,and its application to PEM fuel cell[J].Journal of Alloys and Compounds,2018,741:590-596.). of the Mg phase of an anode is effectively accelerated, but the alloying modification method firstly needs other elements to form an alloy with the Mg phase, and most of the elements do not participate in hydrolysis reaction, so that the theoretical hydrogen release amount is rapidly reduced.
Disclosure of Invention
In order to solve the problem of the prior art that the reaction kinetics of the hydrolysis hydrogen production of Mg is slow, the invention aims to overcome the defects existing in the prior art, and provides a hydrolysis hydrogen production composite material containing Nd 4Mg80Ni8 alloy and pure Mg, a preparation method and application thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
A composite material containing Nd 4Mg80Ni8 alloy and pure Mg for hydrogen production by hydrolysis, wherein the mass percentage of Mg element in the composite material is 65-90%.
Preferably, the phase composition of the Nd 4Mg80Ni8 alloy includes Mg phase, mg 12 Nd phase, and Mg 2 Ni phase.
Preferably, the Mg element accounts for 80-90% of the composite material by mass.
The invention relates to a preparation method of a hydrolytic hydrogen production composite material containing Nd 4Mg80Ni8 alloy and pure Mg, which comprises the following steps:
Step a: mg blocks, nd blocks and Ni blocks with the purity of more than or equal to 99.99 percent are taken as raw materials, the raw materials are mixed according to the element stoichiometric ratio of Nd 4Mg80Ni8 alloy and then are smelted, after the smelting process is repeated for at least three times, molten alloy liquid is poured into a copper mould, and naturally cooled to room temperature, thus obtaining Nd 4Mg80Ni8 alloy;
Step b: and c, carrying out surface treatment on the Nd 4Mg80Ni8 alloy obtained in the step a, removing surface oxides, grinding into powder, mixing with Mg powder, and carrying out ball milling on the mixed powder by adopting a planetary ball mill to obtain the hydrolysis hydrogen production composite material containing the Nd 4Mg80Ni8 alloy and pure Mg.
Preferably, in the step a, a graphite crucible is used, and the mixed raw material is melted in a vacuum high frequency induction furnace.
Preferably, in the step b, specific parameters of the ball milling used are: the rotating speed of the high-energy planetary ball mill is not lower than 350rpm; the ball milling time is 2-4 h.
Preferably, in said step b, the purity of Mg powder is not less than 99.9%.
Preferably, in the step b, the Nd 4Mg80Ni8 alloy powder and the pure Mg powder are mixed and ball-milled, and the mass percentage of the pure Mg powder in the mixture of the Nd 4Mg80Ni8 alloy powder and the pure Mg powder is 42.86-71.43 wt%.
The invention relates to an application of a hydrolytic hydrogen production composite material containing Nd 4Mg80Ni8 alloy and pure Mg, which is applied to the hydrolytic hydrogen production process, and the solid-to-liquid ratio g of hydrolytic hydrogen production material powder containing Nd 4Mg80Ni8 alloy and pure Mg and NaCl solution with the concentration of 3.5 wt.%: the mL was 3:1.
According to the invention, the proportion of Nd 4Mg80Ni8 alloy to pure Mg is changed, the content of Mg element in the x% Mg-Nd 4Mg80Ni8 composite material is controlled, and in the hydrolysis reaction, as potential difference exists between Nd 4Mg80Ni8 alloy and pure Mg, a galvanic corrosion effect is generated, and Nd 4Mg80Ni8 alloy is used as the cathode of a micro-primary cell, so that the corrosion of pure Mg on the anode is accelerated, and the hydrolysis reaction is accelerated. After the pure Mg is completely consumed, the Nd 4Mg80Ni8 alloy begins to hydrolyze, and the Mg 2 Ni phase in the Nd 4Mg80Ni8 alloy acts as a cathode to accelerate corrosion of the Mg phase and Mg 12 Nd phase. In addition, when Nd 4Mg80Ni8 alloy and pure Mg are mixed and ball-milled, cold welding and fracture phenomena can be repeatedly generated through intense impact and collision, so that cracks, defects and lattice distortion which do not exist in Nd 4Mg80Ni8 alloy under the same ball-milling condition are generated, and the phenomena are favorable for the hydrolysis reaction
Compared with the prior art, the invention has the following obvious prominent substantive features and obvious advantages:
1. according to the invention, the Nd 4Mg80Ni8 alloy and pure Mg are compounded by a ball milling method to prepare an x% Mg-Nd 4Mg80Ni8 composite material, and the Nd 4Mg80Ni8 alloy is used as the cathode of the micro-primary cell to accelerate the corrosion of pure Mg on the anode;
2. The invention has simple preparation process and mild hydrogen production condition, and the hydrogen production solution adopts easily available simulated seawater (3.5 wt.%) to provide a hydrogen source for the portable fuel cell.
Drawings
FIG. 1 is an XRD pattern for an x% Mg-Nd 4Mg80Ni8 ball mill for 2 hours for a composite material containing Nd 4Mg80Ni8 alloy and pure Mg according to a preferred embodiment of the invention.
FIG. 2 is a graph showing the hydrolysis of a composite material containing an Nd 4Mg80Ni8 alloy and pure Mg, x% Mg-Nd 4Mg80Ni8, in a 3.5wtNaCl solution at room temperature, according to a preferred embodiment of the invention.
Detailed Description
The foregoing aspects are further described in conjunction with specific embodiments, and the following detailed description of preferred embodiments of the present invention is provided:
Embodiment one:
In the embodiment, the composite material containing Nd 4Mg80Ni8 alloy and pure Mg for hydrogen production by hydrolysis comprises 90% of Mg element by mass percent.
A hydrolysis hydrogen production composite material containing Nd 4Mg80Ni8 alloy and pure Mg, namely a method for producing hydrogen by hydrolysis of a 90% Mg-Nd 4Mg80Ni8 hydrolysis hydrogen production composite material, comprises the following specific steps:
(1) Smelting by using Mg blocks, nd blocks and Ni blocks with the purity of more than or equal to 99.99 percent according to chemical components, repeating the smelting process for three times, pouring the molten alloy into a wedge-shaped copper casting mould, and naturally cooling to room temperature to obtain Nd 4Mg80Ni8 alloy; the alloy contains a Mg phase, a Mg 12 Nd phase and a Mg 2 Ni phase, as shown in figure 1;
(2) Performing surface treatment on the obtained Nd 4Mg80Ni8 alloy to remove surface oxides, and grinding the Nd 4Mg80Ni8 alloy into powder;
(3) Mixing and ball milling Nd 4Mg80Ni8 alloy powder and pure Mg powder according to the proportion of 28.57wt.% and 71.43wt.%, wherein the ball milling speed is 350rpm, and the ball milling time is 2 hours, thus obtaining the 90% Mg-Nd 4Mg80Ni8 composite material.
10ML of simulated seawater was added to 30mg of 90% Mg-Nd 4Mg80Ni8 composite powder at room temperature to carry out hydrolysis hydrogen production reaction, and hydrogen was collected using a drainage method. The hydrogen production curve of the composite material at room temperature is shown in figure 2, the hydrogen release amount of the composite material is 915ml/g within 15min, and the conversion rate is 98%. According to the embodiment, while the alloy galvanic corrosion effect is introduced to improve the yield and the speed of hydrogen production by hydrolysis, the theoretical hydrogen release amount of the system is improved, and the cost of the material is reduced, so that the aim of improving the reaction kinetics and the yield of Mg in the magnesium-based hydrogen production material by hydrolysis is fulfilled.
Embodiment two:
this embodiment is substantially the same as the first embodiment, and is characterized in that:
In the embodiment, the composite material containing Nd 4Mg80Ni8 alloy and pure Mg for hydrogen production by hydrolysis comprises 90% of Mg element by mass percent.
A hydrolysis hydrogen production composite material containing Nd 4Mg80Ni8 alloy and pure Mg, namely a method for producing hydrogen by hydrolysis of a 90% Mg-Nd 4Mg80Ni8 hydrolysis hydrogen production composite material, comprises the following specific steps:
(1) Smelting by using Mg blocks, nd blocks and Ni blocks with the purity of more than or equal to 99.99 percent according to chemical components, repeating the smelting process for three times, pouring the molten alloy into a wedge-shaped copper casting mould, and naturally cooling to room temperature to obtain Nd 4Mg80Ni8 alloy;
(2) Performing surface treatment on the obtained Nd 4Mg80Ni8 alloy to remove surface oxides, and grinding the Nd 4Mg80Ni8 alloy into powder;
(3) Mixing Nd 4Mg80Ni8 alloy powder and pure Mg powder according to the proportion of 28.57% and 71.43%, ball milling, wherein the ball milling speed is 350rpm, and the ball milling time is 4 hours, thus obtaining the 90% Mg-Nd 4Mg80Ni8 composite material.
The 90% mg-Nd 4Mg80Ni8 composite material prepared in this example was ball milled for a longer period of 4 hours. 10mL of simulated seawater was added to 30mg of 90% Mg-Nd 4Mg80Ni8 composite powder at room temperature to carry out hydrolysis hydrogen production reaction, and hydrogen was collected using a drainage method. The hydrogen production curve of the composite material at room temperature is shown in figure 2, the hydrogen release amount of the composite material is 847ml/g within 15min, and the conversion rate is 91%. According to the embodiment, while the alloy galvanic corrosion effect is introduced to improve the yield and the speed of hydrogen production by hydrolysis, the theoretical hydrogen release amount of the system is improved, and the cost of the material is reduced, so that the aim of improving the reaction kinetics and the yield of Mg in the magnesium-based hydrogen production material by hydrolysis is fulfilled.
Embodiment III:
this embodiment is substantially identical to the previous embodiment, except that:
In the embodiment, the composite material containing Nd 4Mg80Ni8 alloy and pure Mg for hydrogen production by hydrolysis comprises 80% of Mg element by mass percent.
A hydrolysis hydrogen production composite material containing Nd 4Mg80Ni8 alloy and pure Mg, namely a 80% Mg-Nd 4Mg80Ni8 hydrolysis hydrogen production composite material hydrolysis hydrogen production method comprises the following specific steps:
(1) Smelting by using Mg blocks, nd blocks and Ni blocks with the purity of more than or equal to 99.99 percent according to chemical components, repeating the smelting process for three times, pouring the molten alloy into a wedge-shaped copper casting mould, and naturally cooling to room temperature to obtain Nd 4Mg80Ni8 alloy;
(2) Performing surface treatment on the obtained Nd 4Mg80Ni8 alloy to remove surface oxides, and grinding the Nd 4Mg80Ni8 alloy into powder;
(3) Mixing Nd 4Mg80Ni8 alloy powder and pure Mg powder according to the proportion, ball milling at the speed of 350rpm for 2 hours to obtain 80% Mg-Nd 4Mg80Ni8 composite material.
10ML of simulated seawater was added to 30mg of 80% Mg-Nd 4Mg80Ni8 composite powder at room temperature to carry out hydrolysis hydrogen production reaction, and hydrogen was collected using a drainage method. The hydrogen production curve of the composite material at room temperature is shown in figure 2, the hydrogen release amount of the composite material is 792ml/g in 15min, and the conversion rate is 96%. The technical effect of the embodiment is that although not outstanding in the previous embodiment, the theoretical hydrogen release amount of the system is improved and the cost of the material is reduced while the yield and the rate of the hydrolysis hydrogen production are improved by introducing the alloy galvanic corrosion effect, so that the aim of improving the reaction kinetics and the yield of Mg in the magnesium-based hydrolysis hydrogen production material is fulfilled.
Embodiment four:
this embodiment is substantially identical to the previous embodiment, except that:
In the embodiment, the composite material containing Nd 4Mg80Ni8 alloy and pure Mg for hydrogen production by hydrolysis comprises 65% of Mg element by mass percent.
The hydrolysis hydrogen production composite material containing Nd 4Mg80Ni8 alloy and pure Mg, namely a method for preparing hydrogen by hydrolysis of 65 percent of Mg-Nd 4Mg80Ni8 hydrolysis hydrogen production composite material, comprises the following specific steps:
(1) And smelting according to chemical components by using Mg blocks, nd blocks and Ni blocks with purity more than or equal to 99.99%, repeating the smelting process for three times, pouring the molten alloy into a wedge-shaped copper casting mould, and naturally cooling to room temperature to obtain the Nd 4Mg80Ni8 alloy.
(2) The obtained Nd 4Mg80Ni8 alloy was subjected to surface treatment to remove surface oxides, and ground into powder.
(3) Mixing and ball milling Nd 4Mg80Ni8 alloy powder and pure Mg powder according to the proportion of 100wt.% and 0wt.%, wherein the ball milling speed is 350rpm, and the ball milling time is 2 hours, thus obtaining 65% Mg-Nd 4Mg80Ni8 composite material.
10ML of simulated seawater was added to 30mg of 65% Mg-Nd 4Mg80Ni8 composite powder at room temperature for hydrolysis hydrogen production reaction, and hydrogen was collected using a drainage method. The hydrogen production curve of the hydrolysis at room temperature is shown in fig. 2, and as can be seen from fig. 2, the hydrogen release amount of the composite material is 643ml/g within 15min, and the conversion rate is 96%. In the embodiment, as pure Mg powder is not added, the catalytic capability of part of active metal is lost in the whole product, and compared with the theoretical hydrogen release amount in the embodiment, the catalytic capability of the active metal is obviously reduced. But still has a higher theoretical hydrogen evolution of the system and reduces the cost of the material.
According to the hydrolytic hydrogen production material compounded by the Nd 4Mg80Ni8 alloy and the pure Mg and the preparation method thereof, the Mg-Nd 4Mg80Ni8 composite material is prepared by mixing and ball milling the Nd 4Mg80Ni8 alloy and the pure Mg, and the 80% Mg-Nd 4Mg80Ni8 and 90% Mg-Nd 4Mg80Ni8 composite material is prepared by changing the component proportion of the Nd 4Mg80Ni8 alloy and the pure Mg, wherein the percentage is the mass percentage of Mg element in the composite material. The embodiment of the invention greatly improves the reaction rate and yield of the magnesium-based hydrolysis hydrogen production material, and the composite material has simple preparation process, low production cost and convenient industrial production.
The embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to the embodiments described above, and various changes, modifications, substitutions, combinations or simplifications made under the spirit and principles of the technical solution of the present invention can be made according to the purpose of the present invention, and all the changes, modifications, substitutions, combinations or simplifications should be equivalent to the substitution, so long as the purpose of the present invention is met, and all the changes are within the scope of the present invention without departing from the technical principles and the inventive concept of the present invention.
Claims (9)
1. A hydrolytic hydrogen production composite material containing Nd 4Mg80Ni8 alloy and pure Mg is characterized in that: the Mg element accounts for 65-90% of the composite material by mass percent; using a ball milling method to enable the Nd 4Mg80Ni8 alloy to have cracks, defects and lattice distortion; in the process of carrying out hydrolysis hydrogen production by using the hydrolysis hydrogen production composite material, nd 4Mg80Ni8 alloy is used as a cathode of a micro-primary cell, pure Mg is used as an anode, and a NaCl solution with the concentration of 3.5wt.% is used as a hydrogen production solution, so that the pure Mg used as the anode generates galvanic corrosion to produce hydrogen; after the pure Mg is completely consumed, the Nd 4Mg80Ni8 alloy begins to hydrolyze, and the Mg 2 Ni phase in the Nd 4Mg80Ni8 alloy acts as a cathode to accelerate corrosion of the Mg phase and corrosion of the Mg 12 Nd phase in the Nd 4Mg80Ni8 alloy, yielding hydrogen.
2. The hydrolytic hydrogen production composite containing Nd 4Mg80Ni8 alloy and pure Mg of claim 1, wherein: the phase composition of the Nd 4Mg80Ni8 alloy includes Mg phase, mg 12 Nd phase, and Mg 2 Ni phase.
3. The hydrolytic hydrogen production composite containing Nd 4Mg80Ni8 alloy and pure Mg of claim 1, wherein: the Mg element accounts for 80-90% of the composite material by mass.
4. A method of preparing a hydrolytic hydrogen production composite containing Nd 4Mg80Ni8 alloy and pure Mg as claimed in claim 1, comprising the steps of:
Step a: mg blocks, nd blocks and Ni blocks with the purity of more than or equal to 99.99 percent are taken as raw materials, the raw materials are mixed according to the element stoichiometric ratio of Nd 4Mg80Ni8 alloy and then are smelted, after the smelting process is repeated for at least three times, molten alloy liquid is poured into a copper mould, and naturally cooled to room temperature, thus obtaining Nd 4Mg80Ni8 alloy;
Step b: and c, carrying out surface treatment on the Nd 4Mg80Ni8 alloy obtained in the step a, removing surface oxides, grinding into powder, mixing with Mg powder, and carrying out ball milling on the mixed powder by adopting a planetary ball mill to obtain the hydrolysis hydrogen production composite material containing the Nd 4Mg80Ni8 alloy and pure Mg.
5. The method for preparing the composite material containing Nd 4Mg80Ni8 alloy and pure Mg for hydrogen production by hydrolysis, which is characterized in that: in the step a, a graphite crucible is used, and the mixed raw material is melted in a vacuum high-frequency induction furnace.
6. The method for preparing the composite material containing Nd 4Mg80Ni8 alloy and pure Mg for hydrogen production by hydrolysis, which is characterized in that: in the step b, the specific parameters of the ball milling adopted are as follows: the rotating speed of the high-energy planetary ball mill is not lower than 350 rpm; the ball milling time is 2-4 h.
7. The method for preparing the composite material containing Nd 4Mg80Ni8 alloy and pure Mg for hydrogen production by hydrolysis, which is characterized in that: in the step b, the purity of the Mg powder is not less than 99.9%.
8. The method for preparing the composite material containing Nd 4Mg80Ni8 alloy and pure Mg for hydrogen production by hydrolysis, which is characterized in that: in the step b, nd 4Mg80Ni8 alloy powder and pure Mg powder are mixed and ball-milled, and the mass percentage content of the pure Mg powder in the mixture of Nd 4Mg80Ni8 alloy powder and pure Mg powder is 42.86-71.43 wt%.
9. Use of a hydrolytic hydrogen production composite containing Nd 4Mg80Ni8 alloy and pure Mg as claimed in claim 1, characterized in that: the solid-to-liquid ratio g of the powder of the hydrolytic hydrogen production material containing Nd 4Mg80Ni8 alloy and pure Mg and the NaCl solution with the concentration of 3.5wt.% is applied to the hydrolytic hydrogen production process: the mL was 3:1.
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| CA2217095A1 (en) * | 1997-10-22 | 1999-04-22 | Hydro-Quebec | Activated interface nanocomposites prepared by mechanical grinding of magnesium hydrides and their use for hydrogen storage |
| US6478844B1 (en) * | 1999-12-13 | 2002-11-12 | Energy Conversion Devices, Inc. | Method for making hydrogen storage alloy |
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