CN111825507A - Al-LiH composite fuel for unmanned underwater vehicle and preparation method thereof - Google Patents
Al-LiH composite fuel for unmanned underwater vehicle and preparation method thereof Download PDFInfo
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- CN111825507A CN111825507A CN202010580432.XA CN202010580432A CN111825507A CN 111825507 A CN111825507 A CN 111825507A CN 202010580432 A CN202010580432 A CN 202010580432A CN 111825507 A CN111825507 A CN 111825507A
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
- C06D5/10—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of solids with liquids
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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
- C01B3/065—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 from a hydride
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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
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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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Abstract
The invention provides an Al-LiH composite fuel for an unmanned underwater vehicle and a preparation method thereof, belonging to the technical field of fuels for underwater vehicles. The Al-LiH composite fuel is powder comprising main phase aluminum (Al) and dispersed phase lithium hydride (LiH), wherein the LiH is uniformly dispersed in the aluminum powder. During preparation, the Al-LiH composite fuel is prepared by weighing aluminum powder and lithium hydride, uniformly mixing, putting into a ball milling tank, sealing and then ball milling in a ball mill. The Al-LiH composite fuel prepared by the invention has micro-explosion performance when being subjected to combustion reaction with high-temperature steam, and can continuously remove Al on the surface of Al powder2O3Therefore, the fuel has the characteristics of high energy, high density, quick start with water, efficient combustion and high hydrogen production.
Description
Technical Field
The invention belongs to the technical field of fuels for underwater vehicles, and particularly relates to an Al-LiH composite fuel for an unmanned underwater vehicle and a preparation method thereof.
Background
The ocean is very important to the strategic significance of China, various high-tech means are needed for the development and utilization of ocean resources, the maintenance of the ocean rights and interests of China and the like, and sophisticated technologies are needed for safeguarding the national security and building the strong ocean. The underwater vehicle technology is an important means for realizing the purposes, and is a field which is paid attention to by all countries.
The power system determines the overall design and endurance of the underwater vehicle, and the endurance, the navigation depth, the navigation speed and the carrying amount of the sensors are determined by the energy and the performance of the power system. The underwater hybrid power system based on aluminum/water combustion has the characteristics of high energy density and long-time operation, the required oxidant can be taken from seawater, the oxidant and the oxidant storage tank are omitted in the system, and H is generated after reaction2The characteristics of being used for fuel cells or recycled are the hot spots of research in various countries in recent years.
The aluminum powder is supplied primarily as a carrier gas/carrier liquid feed. The adoption of the carrier gas/carrier liquid feeding mode means that aluminum powder is dispersed in high-pressure carrier gas or carrier liquid, and then enters the combustion chamber along with the high-pressure carrier gas/carrier liquid to react with water vapor violently, because the space occupied by the high-pressure carrier gas/carrier liquid is small, the content of the aluminum powder entering the combustion chamber is high, and the performance of a power system is improved. However, the metal fuel entering the combustion chamber has a low initial combustion temperature, so that the aluminum powder is difficult to react with water at a low temperature, and the aluminum powder is melted only when the oxide film on the surface of the aluminum powder is more than 2600K, so that the aluminum powder is heated to a molten or gasified state and then enters the combustion chamber to rapidly react with high-temperature water vapor to release a large amount of heat and generate a large amount of hydrogen. However, the system is complicated, and the underwater vehicle with high structural compactness and high power system requirement is fatally attacked.
The existing research shows that the combustion conversion rate of the metallic aluminum and water is not high, and the main reasons are as follows:
(1) the aluminum is very active and has high reaction activity, and is easily oxidized when being placed in the air, and a compact oxide film generated on the surface prevents the reaction from going on;
(2) al generated by combustion with water even if the surface oxide film is removed2O3The aluminum oxide can be continuously attached to the surface of unreacted aluminum, so that the continuous reaction is hindered, and the reaction rate and the reaction conversion rate are reduced; the reaction starting of the micron-grade metal aluminum powder and water is very difficult, and the reaction of the aluminum powder and water vapor can be considered to occur at a high temperature of about 1000 ℃;
(3) in order to improve the reaction activity, nano aluminum powder is used for research, but the nano aluminum powder has large specific surface area and low active aluminum content, so that the energy performance of a propulsion system is reduced, meanwhile, the nano aluminum powder has an agglomeration phenomenon, and the cost is greatly increased (about 20-50 times of that of micron aluminum powder) compared with that of micron aluminum powder.
Therefore, how to remove the oxide on the surface of the aluminum powder and realize the continuous and efficient combustion of the aluminum powder and water in the reaction process is a key and difficult point of domestic and foreign research and is also a key technology which needs to be solved firstly by an advanced underwater power system.
Disclosure of Invention
The present invention has been made in view of the above-mentioned problems of the conventional hybrid system based on the aluminum/water combustion reaction, and an object of the present invention is to provide a fuel which has high energy, high density, rapid start with water, high combustion efficiency, and a large hydrogen production amount, and a method for preparing the same.
The design idea of the invention is as follows: lithium hydride (LiH) is dispersed and distributed in aluminum (Al) particles through ball milling, and the Al-LiH composite fuel with micro-explosion performance in the combustion reaction process with water is prepared. H is released by the rapid reaction of LiH and water2The Al-LiH particles are continuously burst into smaller particles, fresh aluminum is continuously exposed on the surface of the powder and the specific surface area of the reaction is increased, and simultaneously, the product lithium hydroxide (LiOH) after the reaction of the LiH and the water can react with aluminum oxide (Al)2O3) Further reaction continuously removes oxides on the surface of the aluminum powder in the reaction process to increase the reaction channel of the fresh Al and water inside, thereby improving the combustion efficiency of the Al powder and providing technical support for an underwater hybrid power system.
The technical scheme provided by the invention is as follows:
in a first aspect, an Al-LiH composite fuel is a powder comprising a main phase of aluminum (Al) and a dispersed phase of lithium hydride (LiH), wherein the LiH is dispersed in the aluminum powder.
In a second aspect, a method for preparing an Al-LiH composite fuel according to the first aspect includes: weighing aluminum powder and lithium hydride, uniformly mixing, putting into a ball mill tank, sealing, and ball milling in a ball mill to obtain the Al-LiH composite fuel.
The Al-LiH composite fuel for the unmanned underwater vehicle and the preparation method thereof provided by the invention have the following beneficial effects:
in the invention, the LiH is dispersed and distributed in the Al particles to prepare the Al-LiH composite fuel with micro-explosion performance in the combustion reaction process with water. H is released by the rapid reaction of LiH and water2The Al-LiH particles are continuously cracked into smaller particles, fresh aluminum is continuously exposed on the surface of the powder and the specific surface area of the reaction is increased, and meanwhile, the product LiOH after the reaction of the LiH and the water can react with Al2O3Further reaction continuously removes oxides on the surface of the aluminum powder in the reaction process to increase the reaction channel of fresh Al and water inside, so that the combustion efficiency of the Al powder is improved, and the obtained Al-LiH composite fuel has high energy and high density, can be quickly started with water, can be efficiently combusted, and has high hydrogen production.
Drawings
Fig. 1 is an SEM electron micrograph of the Al — LiH composite fuel in example 4 prepared by the ball milling method.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
According to a first aspect of the present invention, there is provided an Al-LiH composite fuel for unmanned underwater vehicles, which is a powder comprising a main phase aluminum (Al) and a dispersed phase lithium hydride (LiH), wherein the LiH is dispersed in the Al powder.
Preferably, the Al — LiH composite fuel is a powder composed of a main phase of aluminum and a dispersed phase of lithium hydride. The mass percentages of Al and LiH are as follows:
50 to 97 percent of Al; preferably 70-97%, 80-95%.
LiH, the balance being preferably 3 to 50%.
In the present invention, the median particle diameter D50 of the Al-LiH composite fuel is 0.1 to 50 μm. The particle size is crucial to the combustion performance and the energy performance of the composite fuel, if the particle size is too small and is lower than the required range, the activity of the powder is too strong, and the powder is easy to react with oxygen, water vapor and the like in the air in the processes of storage and use to influence the energy performance of the composite fuel; if the particle size is too large and exceeds the required range, the combustion efficiency is impaired.
In the invention, the conversion rate of the combustion reaction of the Al-LiH composite fuel and high-temperature water vapor can reach 83.0-98.5%.
According to a second aspect of the present invention, there is provided a method for producing an Al-LiH composite fuel for an unmanned underwater vehicle, for producing the Al-LiH composite fuel according to the first aspect, comprising: weighing aluminum powder and lithium hydride, uniformly mixing, putting into a ball mill tank, sealing, and ball milling in a ball mill to obtain the Al-LiH composite fuel.
Wherein the aluminum powder is micron aluminum powder, and the specification of the micron aluminum powder is any one or a combination of several of FLQT1 (median particle size of 29 +/-3 mu m), FLQT2 (median particle size of 24 +/-3 mu m), FLQT3 (median particle size of 13 +/-2 mu m), FLQT4 (median particle size of 6 +/-1.5 mu m) and FLQT5 (median particle size of 2 +/-1 mu m).
Wherein, the lithium hydride is micron-sized, and the median particle diameter D50 is 1-2 μm.
In the invention, the ball mill is any one of a planetary ball mill, a horizontal ball mill or a conical ball mill.
During grinding, the ball-material ratio (namely the mass ratio of grinding balls to materials of the ball mill) is (10-50): 1.
the rotating speed of the ball mill is 200 r/min-400 r/min, and the ball milling time is 30 min-10 h.
Researches show that the particle sizes, the rotating speeds and the ball milling time of the aluminum powder and the lithium hydride are very related to the dispersion state of the LiH in the Al powder, the particle sizes of the aluminum powder and the lithium hydride are in the range, and the LiH can be dispersed and distributed in the Al powder by optimizing the ball milling process. If the rotating speed is lower than the range and the ball milling time is shorter than the range, LiH is difficult to disperse in Al powder; if the rotating speed is higher than the range and the ball milling time is longer than the range, the particle size is too small, the specific surface area of the aluminum powder is large, the aluminum powder is easy to oxidize, and the combustion efficiency is low.
Examples
Example 1
In the glove box, 9.7g of FLQT5 aluminum powder and 0.3g of LiH (D50 is 2 microns) are uniformly mixed and poured into a ball milling tank, the ball milling tank is sealed and then taken out, ball milling is carried out on a planetary ball mill for 30min at the rotating speed of 200r/min, and the ball-material ratio is 50: 1, preparing the Al-LiH composite fuel with the median particle size of 2 mu m. The density of the Al-LiH composite fuel is measured: 2.52g/cm3And the conversion rate of the combustion reaction with high-temperature water vapor is as follows: 83.0 percent and 30MJ/kg of oxygenated combustion heat.
Example 2
5g of FLQT3 aluminum powder and 5g of LiH (D50 is 1.5 mu m) are uniformly mixed in a glove box, poured into a ball milling tank, sealed and taken out, ball milled for 5 hours on a planetary ball mill at the rotating speed of 300r/min, and the ball-to-material ratio is 40: 1, preparing the Al-LiH composite fuel with the median particle size of 5 mu m. The density of the Al-LiH composite fuel is measured: 1.23g/cm3And the conversion rate of the combustion reaction with high-temperature water vapor is as follows: 98.5 percent and the oxygenated combustion heat is 33.8 MJ/kg.
Example 3
In the glove box, 7.35g of FLQT1 aluminum powder and 2.65g of LiH (D50 is 2 microns) are uniformly mixed and poured into a ball milling tank, the ball milling tank is sealed and then taken out, ball milling is carried out on a planetary ball mill for 7 hours at the rotating speed of 400r/min, and the ball-material ratio is 15: 1, preparing the Al-LiH composite fuel with the median particle size of 22 mu m. The density of the Al-LiH composite fuel is measured: 1.65g/cm3And the conversion rate of the combustion reaction with high-temperature water vapor is as follows: 96.3 percent and oxygenated combustion heat of 32.1 MJ/kg.
Example 4
Uniformly mixing 45g of FLQT1 aluminum powder and 5g of LiH (D50 is 2 microns) in a glove box, pouring the mixture into a ball milling tank, sealing the ball milling tank, taking out the ball milling tank, and performing ball milling on a planetary ball mill for 10 hours at the rotating speed of 300r/min, wherein the ball-to-material ratio is 30: 1, preparing the Al-LiH composite fuel, wherein the median particle size is 11 mu m, and an SEM electron micrograph is shown in figure 1. The density of the Al-LiH composite fuel is measured: 2.18g/cm3Is high and highConversion rate of warm water steam combustion reaction: 94 percent and 31.2MJ/kg of oxygenated combustion heat.
Example 5
30g of FLQT3 aluminum powder and 20g of LiH (D50 is 1 mu m) are uniformly mixed in a glove box, poured into a ball milling tank, sealed and taken out, ball-milled for 8 hours on a planetary ball mill at the rotating speed of 200r/min, and the ball-to-material ratio is 10: 1, preparing the Al-LiH composite fuel with the median particle size of 32 mu m. The density of the Al-LiH composite fuel is measured: 1.38g/cm3And the conversion rate of the combustion reaction with high-temperature water vapor is as follows: 98 percent and the heat of oxygenation combustion is 32.9 MJ/kg.
Example 6
32.5g of FLQT3 aluminum powder and 17.5g of LiH (D50 is 2 mu m) are uniformly mixed in a glove box, poured into a ball milling tank, sealed and taken out, and ball milled for 2 hours on a planetary ball mill at the rotating speed of 250r/min, wherein the ball-material ratio is 20: 1, preparing the Al-LiH composite fuel with the median particle size of 47 mu m. The density of the Al-LiH composite fuel is measured: 1.47g/cm3And the conversion rate of the combustion reaction with high-temperature water vapor is as follows: 97.5 percent and the oxygen-enriched combustion heat is 33.0 MJ/kg.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Those skilled in the art will appreciate that those matters not described in detail in the present specification are well known in the art.
Claims (10)
1. The Al-LiH composite fuel is characterized by comprising main phase aluminum (Al) and dispersed phase lithium hydride (LiH) powder, wherein the LiH is dispersed in the aluminum powder.
2. The composite fuel of claim 1, wherein the mass percentages of Al and LiH in the composite fuel are:
Al:50％～97％；
LiH, the balance.
3. The composite fuel of claim 2, wherein the mass percentages of Al and LiH in the composite fuel are:
Al:70％～97％；
LiH, the balance.
4. The composite fuel of claim 3, wherein the mass percentages of Al and LiH in the composite fuel are:
Al:80％～95％；
LiH, the balance.
5. The composite fuel according to claim 1, wherein the Al-LiH composite fuel is a powder composed of a main phase of aluminum and a dispersed phase of lithium hydride.
6. The composite fuel according to claim 1, wherein the median particle diameter of the Al-LiH composite fuel is 0.1 μm to 50 μm.
7. A method for producing an Al-LiH composite fuel, characterized by comprising, for producing the Al-LiH composite fuel according to any one of claims 1 to 6: weighing aluminum powder and lithium hydride, uniformly mixing, putting into a ball mill tank, sealing, and ball milling in a ball mill to obtain the Al-LiH composite fuel.
8. The preparation method of claim 7, wherein the aluminum powder is micron aluminum powder selected from one or more of FLQT1, FLQT2, FLQT3, FLQT4 and FLQT5, wherein the median particle size of FLQT1 aluminum powder is 29 +/-3 μm, the median particle size of FLQT2 aluminum powder is 24 +/-3 μm, the median particle size of FLQT3 aluminum powder is 13 +/-2 μm, the median particle size of FLQT4 aluminum powder is 6 +/-1.5 μm, and the median particle size of FLQT5 aluminum powder is 2 +/-1 μm.
9. The method of claim 7, wherein the lithium hydride is a micron-sized lithium hydride having a median particle size of 1 μm to 2 μm.
10. The preparation method according to claim 7, wherein the ball-to-feed ratio is (10-50): 1; and/or
The rotating speed of the ball mill is 200 r/min-400 r/min, and the ball milling time is 30 min-10 h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114032127A (en) * | 2021-08-26 | 2022-02-11 | 湖北航天化学技术研究所 | High-energy-density slurry fuel, preparation method and application |
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2020
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114032127A (en) * | 2021-08-26 | 2022-02-11 | 湖北航天化学技术研究所 | High-energy-density slurry fuel, preparation method and application |
| CN114032127B (en) * | 2021-08-26 | 2022-12-27 | 湖北航天化学技术研究所 | High-energy-density slurry fuel, preparation method and application |
| WO2023025265A1 (en) * | 2021-08-26 | 2023-03-02 | 湖北航天化学技术研究所 | High-energy-density slurry fuel, preparation method, and application |
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Application publication date: 20201027 |