CN112296330B - Real-time hydrogen production aluminum-based composite material with low-temperature activity and preparation method thereof - Google Patents

Real-time hydrogen production aluminum-based composite material with low-temperature activity and preparation method thereof Download PDF

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CN112296330B
CN112296330B CN202011121322.3A CN202011121322A CN112296330B CN 112296330 B CN112296330 B CN 112296330B CN 202011121322 A CN202011121322 A CN 202011121322A CN 112296330 B CN112296330 B CN 112296330B
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hydrogen production
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CN112296330A (en
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王辉虎
苏明
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Hubei University of Technology
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    • B22F1/0003
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/04Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06Production 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
    • C01B3/08Production 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/04Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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  • Organic Chemistry (AREA)
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  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention provides a novel alloy with lowThe warm-active real-time hydrogen production aluminum-based composite material and the preparation method thereof can realize the real-time and high-efficiency hydrogen production in the aqueous solution of 23wt% NaCl at the low temperature of 20 ℃ below zero, the conversion efficiency of hydrogen production reaches 84.5%, which is far higher than the conversion efficiency of the existing hydrogen production aluminum alloy at low temperature, and no reaction lag time, thereby bringing opportunities for the application of the aluminum water hydrogen production in plateau areas and cold areas. The invention provides a preparation method of a real-time hydrogen production aluminum-based composite material with low-temperature activity, which is characterized by comprising the following steps: the raw materials comprise the following components in percentage by mass: 70-95 wt.% Al, 1-3 wt.% Ga, 1-3 wt.% In, 2-5wt.% Sn, 5-10 wt.% NaCl, 3-5 wt.% g-C 3 N 4 0.5-15wt% of LiH, and ball milling the raw materials to obtain the real-time hydrogen production aluminum-based composite material with low-temperature activity.

Description

Real-time hydrogen production aluminum-based composite material with low-temperature activity and preparation method thereof
Technical Field
The invention belongs to the field of hydrogen production by metal hydrolysis, and particularly relates to a real-time hydrogen production aluminum-based composite material with low-temperature activity and a preparation method thereof.
Technical Field
In recent years, with the increasing exhaustion of fossil energy and environmental pollution, green energy is urgently needed to replace traditional fossil fuel with serious environmental pollution in countries around the world. The hydrogen is an ideal green sustainable energy source, the energy density of hydrogen per unit mass is about 2.8 times of that of natural gas and 5 times of that of coal, and the method also has the advantages of wide sources, high conversion efficiency and cleanness, and the reaction product is only water. Two major problems of the current hydrogen energy industry are hydrogen production and hydrogen storage. The industrial hydrogen production method mainly utilizes coal, petroleum, natural gas and other fossil energy sources for cracking production, however, the method not only consumes fossil fuel, but also causes certain pollution to the environment. In addition, the hydrogen production from coke oven gas or industrial purge gas is less costly but limited by location, scale, transport radius, etc. The transportation mode of the hydrogen comprises a hydrogen special pipeline, compressed hydrogen, liquefied hydrogen, a liquid organic hydrogen carrier, a metal alloy hydrogen storage mode and the like. The density of hydrogen is extremely low, and the volumetric energy density of compressed hydrogen is not high, so that the storage and transportation efficiency of the method adopting compressed hydrogen is low, which means high cost. The liquefaction temperature of the hydrogen is-253 ℃, the problems of continuous gasification and pressure rise of the liquid hydrogen need to be solved when the liquid hydrogen is transported for a long distance, and the problem has huge potential safety hazards. The real safe use of the hydrogen energy is real-time preparation and use, and the intermediate storage and transportation links are reduced.
The hydrogen production by metal hydrolysis is a hot spot of the current real-time hydrogen production research, and mainly comprises alkali metal, magnesium-based and aluminum-based composite materials and the like. The metallic aluminum is active in property, is the metallic element with the largest content in the earth crust, has small density and high specific energy, has great thermodynamic tendency for generating hydrogen by reacting with water, but easily forms a compact oxide film on the surface of the metallic aluminum to hinder the reaction from proceeding. Meanwhile, when the temperature is reduced, the reaction lag time generally exists in the aluminum water reaction, and the hydrogen production conversion efficiency is reduced. In addition, the freezing point of water is 0 ℃, and when the temperature is lower than 0 ℃, how to realize the real-time high-efficiency aluminum water reaction hydrogen production is an actual problem to be solved urgently, and the method has important significance for the application of the technology in plateau areas and cold areas.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a real-time hydrogen production aluminum-based composite material having low-temperature activity, which can realize high-efficiency hydrogen production in a 23wt% aqueous solution of nacl at a low temperature of-20 ℃, and a method for producing the same.
In order to achieve the purpose, the invention adopts the following scheme:
< method >
The invention provides a preparation method of a real-time hydrogen production aluminum-based composite material with low-temperature activity, which is characterized by comprising the following steps: the raw materials comprise the following components in percentage by mass: 70-95 wt.% Al, 1-3 wt.% Ga, 1-3 wt.% In, 2-5wt.% Sn, 5-10 wt.% NaCl, 3-5 wt.% g-C 3 N 4 0.5-15wt% of LiH, and ball-milling the raw materials to obtain the real-time hydrogen production aluminum-based composite material with low-temperature activity.
Preferably, the real-time hydrogen production aluminum-based composite material with low-temperature activity and the preparation method thereof provided by the invention can also have the following characteristics: the raw materials comprise the following components in percentage by weight: 75 to 92wt.% of Al,1 to 3wt.% of Ga,1 to 3wt.% of In,3 to 5wt.% of Sn,5 to 10wt.% of NaCl,3 to 5wt.% of g-C 3 N 4 0.5-3wt% of LiH, the proportioning effect is better.
Preferably, the real-time hydrogen production aluminum-based composite material with low-temperature activity and the preparation method thereof provided by the invention can also have the following characteristics: the raw materials comprise the following components in percentage by weight: 78wt.% Al,1.5wt.% Ga,1.5wt.% In,4wt.% Sn,9wt.% NaCl,4.5wt.% g-C 3 N 4 1.5wt.% LiH, the best effect of the mixture ratio.
Preferably, the real-time hydrogen production aluminum-based composite material with low-temperature activity and the preparation method thereof provided by the invention can also have the following characteristics: g-C 3 N 4 The melamine is prepared by burning melamine at 550 ℃ for 2 hours.
Preferably, the real-time hydrogen production aluminum-based composite material with low-temperature activity and the preparation method thereof provided by the invention can also have the following characteristics: the ball milling process is carried out under the protection of inert gas, and the inert gas is nitrogen or argon.
Preferably, the real-time hydrogen production aluminum-based composite material with low-temperature activity and the preparation method thereof provided by the invention can also have the following characteristics: the mass ratio of ball materials subjected to ball milling is 10-15, and the mass ratio of big balls to small balls is 1.
Preferably, the real-time hydrogen production aluminum-based composite material with low-temperature activity and the preparation method thereof provided by the invention can also have the following characteristics: the ball milling time is 6-12 h.
Preferably, the real-time hydrogen production aluminum-based composite material with low-temperature activity and the preparation method thereof provided by the invention can also have the following characteristics: the main shaft rotating speed of the ball mill is more than 360r/min.
Preferably, the real-time hydrogen production aluminum-based composite material with low-temperature activity and the preparation method thereof provided by the invention can also have the following characteristics: and storing the real-time hydrogen production aluminum-based composite material with low-temperature activity by adopting vacuum packaging after ball milling.
< materials >
The invention also provides a real-time hydrogen production aluminum-based composite material with low-temperature activity, which is characterized in that: the preparation method described in the above < method > was used.
Action and Effect of the invention
The invention provides a real-time hydrogen production aluminum-based composite material with low-temperature activity and a preparation method thereof, aiming at solving the application problem of hydrogen production from aluminum water in a low-temperature environment, wherein the aluminum-based composite material is prepared by NaCl and g-C 3 N 4 And LiH, can produce hydrogen in real time at-20 ℃ and 23wt% of NaCl aqueous solution, and the maximum hydrogen production rate reaches110 ml. GAl -1 ·s -1 The conversion efficiency of hydrogen production can reach 88 percent, is far higher than the conversion efficiency of the existing hydrogen-producing aluminum alloy at low temperature, has no reaction lag time, can produce hydrogen in real time, brings opportunities for the application of the aluminum water hydrogen production in plateau areas and cold areas, and has simple preparation process, low cost and good industrial application prospect.
Detailed Description
Specific embodiments of the real-time hydrogen production aluminum-based composite material having low-temperature activity and the method for producing the same according to the present invention will be described in detail below.
In the following examples, g-C 3 N 4 Is prepared by burning melamine at 550 ℃ for 2 hours. The method for collecting hydrogen gas during hydrolysis of the aluminum-based composite material is a drainage method, a weighed sample (containing 1g of active aluminum) is poured into a three-neck flask containing 23wt.% of NaCl aqueous solution at the temperature of minus 20 ℃, a rubber plug is covered, and the amount of hydrogen gas generated is recorded by the drainage method.
< example one >
The preparation method of the real-time hydrogen production aluminum-based composite material with low-temperature activity provided by the embodiment comprises the following steps: 81wt.% of Al powder, 2wt.% of Ga, 2wt.% of In powder, 3.5wt.% of Sn powder, 6wt.% of NaCl, 5wt.% of g-C 3 N 4 And 0.5wt.% LiH as a raw material, the ball-to-feed ratio is 10, and the size-to-ball ratio is 1. Ball milling is carried out for 8h by a planetary ball mill, and the rotating speed is 360r/min. After the ball milling is finished, opening the ball milling tank in a vacuum glove box, then taking out the prepared hydrolysis hydrogen production aluminum-based composite material sample, and putting the sample into a sealing bag for vacuum storage.
< example two >
The difference from the first embodiment is only that the following raw materials are adopted: 80wt.% Al powder, 1.5wt.% Ga, 2wt.% In powder, 4wt.% Sn powder, 7wt.% NaCl,4.5wt.% g-C 3 N 4 And 1wt.% LiH.
< example three >
The difference from the first embodiment is only that the following raw materials are adopted: 78wt.% Al powder, 1.5wt.% Ga,1.5wt.% In powder, 4wt.% Sn powder, 9wt.% NaCl,4.5wt.% g-C 3 N 4 And 1.5wt.% LiH, the ball milling time was 12h, and the rotation speed was 420r/min.
< example four >
The difference from the first embodiment is only that the following raw materials are adopted: 75wt.% Al powder, 2wt.% Ga, 2wt.% In powder, 4.5wt.% Sn powder, 10wt.% NaCl,4.5wt.% g-C 3 N 4 And 2wt.% of LiH, wherein the ball-material ratio is 12, the ball milling time is 12h, and the rotating speed is 450r/min.
<Comparative example 1>(without addition of NaCl, g-C 3 N 4 And LiH)
The difference from the first embodiment is only that the following raw materials are adopted: 92wt.% Al powder, 2wt.% Ga powder, 2wt.% In powder, 4wt.% Sn powder.
<Comparative example II>(without addition of g-C 3 N 4 And LiH)
The difference from the first embodiment is only that the following raw materials are adopted: 83wt.% of Al powder, 1.5wt.% of Ga,1.5wt.% of In powder, 4wt.% of Sn powder, 10wt.% of NaCl.
< comparative example III > (without addition of LiH)
The difference from the first embodiment is only that the following raw materials are adopted: 83wt.% Al powder, 1.5wt.% Ga,1.5wt.% In powder, 3wt.% Sn powder, 6wt.% NaCl, and 5wt.% g-C 3 N 4
<Comparative example four>(without addition of g-C 3 N 4 )
The difference from the first embodiment is only that the following raw materials are adopted: 81wt.% of Al powder, 1.5wt.% of Ga,1.5wt.% of In powder, 4wt.% of Sn powder, 10wt.% of NaCl and 2wt.% of LiH, wherein the ball-milling ratio is 15.
<Comparative example five>(without addition of NaCl and g-C 3 N 4 )
The difference from the first embodiment is only that the following raw materials are adopted: 79wt.% of Al powder, 1.5wt.% of Ga,1.5wt.% of In powder, 3wt.% of Sn powder and 15wt.% of LiH.
Performance test conditions:
in each of the examples and comparative examples, a certain amount of a sample of a hydrogen-producing aluminum-based composite material (each containing 1g of activated aluminum) was charged into a three-necked flask containing 23wt.% deionized water at-20 ℃, and the amount of hydrogen produced by hydrolysis was recorded by draining, and the results are shown in table 1 below.
TABLE 1 The 23wt% of NaCl solution for hydrogen production at-20 deg.C is through-solution for hydrogen production
Figure BDA0002732092710000051
The results show that: example three has the maximum hydrogen production rate, which reaches 110 ml. GAl -1 ·s -1 And all LiH-added samples reacted directly in aqueous NaCl solution at-20 ℃ 23wt% without lag time. Comparative example No addition of g-C 3 N 4 In the case of (3), although the reaction does not delay, the amount of hydrogen produced is very low. Comparative example five No addition of NaCl and g-C 3 N 4 In the case of (2), liH reacts instantaneously, but Al does not react substantially, and the hydrogen production is only by hydrolysis of LiH, and the conversion efficiency is extremely low. As can be confirmed by the above examples and comparative examples, the aluminum matrix composite prepared by the method is prepared by NaCl, g-C 3 N 4 And LiH, and has the excellent performance of producing hydrogen in real time and high efficiency at the temperature of minus 20 ℃, and the real-time high-efficiency hydrogen production of the aluminum-based composite material in a low-temperature environment has great significance for the application of aluminum water hydrogen production in plateau areas and cold areas.
The above embodiments are merely illustrative of the technical solutions of the present invention. The real-time hydrogen production aluminum-based composite material with low temperature activity and the preparation method thereof according to the present invention are not limited to the contents described in the above embodiments, but are subject to the scope defined by the claims. Any modification, or addition, or equivalent replacement by a person skilled in the art on the basis of this embodiment is within the scope of the invention as claimed in the claims.

Claims (8)

1. A preparation method of a real-time hydrogen production aluminum-based composite material with low-temperature activity is characterized by comprising the following steps:
the raw materials comprise: 78wt.% Al,1.5wt.% Ga,1.5wt.% In,4wt.% Sn,9wt.% NaCl,4.5wt.% g-C 3 N 4 ,1.5wt.% LiH;
And performing ball milling on the raw materials to obtain the real-time hydrogen production aluminum-based composite material with low-temperature activity.
2. The method for preparing the aluminum-based composite material with low-temperature activity for real-time hydrogen production according to claim 1, wherein the method comprises the following steps:
wherein, g-C 3 N 4 The melamine is prepared by burning melamine at 550 ℃ for 2 hours.
3. The method for preparing the aluminum-based composite material with low-temperature activity for real-time hydrogen production according to claim 1, wherein the method comprises the following steps:
wherein, the ball milling process is carried out under the protection of inert gas.
4. The method for preparing the aluminum-based composite material with low-temperature activity for real-time hydrogen production according to claim 1, wherein the method comprises the following steps:
the mass ratio of ball materials subjected to ball milling is 10 to 15, and the mass ratio of big balls to small balls is 1.
5. The method for preparing the aluminum-based composite material with low-temperature activity for real-time hydrogen production according to claim 1, wherein the method comprises the following steps:
wherein the ball milling time is 6 to 12h.
6. The method for preparing the aluminum-based composite material with low-temperature activity for real-time hydrogen production according to claim 1, wherein the method comprises the following steps:
wherein the ball milling speed is more than 360r/min.
7. The method for preparing the aluminum-based composite material for real-time hydrogen production with low-temperature activity according to claim 1, which is characterized in that:
and after ball milling, storing the real-time hydrogen production aluminum-based composite material with low-temperature activity by adopting vacuum packaging.
8. A real-time hydrogen production aluminum-based composite material with low-temperature activity is characterized in that:
prepared by the preparation method of any one of claims 1 to 7.
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