CN106191541A - A kind of hydrolytic hydrogen production aluminium alloy and preparation method thereof - Google Patents
A kind of hydrolytic hydrogen production aluminium alloy and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of hydrolytic hydrogen production aluminium alloy and preparation method thereof.The present invention uses Mechanical Alloying, with include following mass content component as raw material: Al 60～97wt%, Ga 0.5～10wt%, In0.5～10wt%, Sr 0.5～10wt%, SnCl21～10wt%, carry out the hydrolytic hydrogen production aluminium alloy that ball milling obtains having good hydrogen manufacturing performance.Test result indicate that, the hydrolytic hydrogen production aluminium alloy prepared of preparation method that the present invention provides can direct reaction after contacting with water at normal temperatures, there is no Lag time, hydrogen output is up to 1210mL/g, produce hydrogen rate up to 97.3%, real-time hydrogen manufacturing and real-time hydrogen supply can be reached, it is adaptable to provide high-purity hydrogen source for hydrogen-oxygen fuel cell automobile.The preparation method that the present invention provides is with low cost, simple to operation, it is adaptable to industrialized production.
Description
Technical field
The present invention relates to technical field of metal, particularly to a kind of hydrolytic hydrogen production aluminium alloy and preparation method thereof.
Background technology
The energy is that human society is depended on for existence and the important basis constantly advanced and guarantee, energy shortage and environment
Polluting and become two hang-ups that contemporary mankind's social development faces, present stage world energy sources is constituted or with coal, oil, natural
The gas three great tradition energy is main.Owing to these Fossil fuels are non-renewable, develop clean energy resource extremely urgent.Hydrogen Energy
Energy density is higher, and oxidation reaction product only has water, is a kind of more satisfactory fuel.Effectively utilizing of Hydrogen Energy can alleviate energy
Source crisis, reduce environmental pollution and promote regenerative resource and develop, be considered 21 century the most potential cleaning energy
Source.Therefore, the large-scale application of Hydrogen Energy meets the theory that " green " is developed, for the whole world recycling economy and human society can
Sustainable development tool is of great significance.
At present, Hydrogen Energy industrialization is limited by three aspects such as hydrogen producing technology, hydrogen storage technology and fortune hydrogen technology and is difficult to extensively
Implement.Hydrogen manufacturing aspect, currently mainly has water electrolysis hydrogen production, Fossil fuel reformation hydrogen production and three kinds of hydrogen production process of biological hydrogen production, electricity
Solve one of water ripe and widely used technology of hydrogen manufacturing one Technical comparing.Although the cost of the raw material needed for water electrolysis hydrogen production is relatively
Low, but water electrolysis hydrogen production needs to consume electric energy and energy consumption is relatively big, thus restrict its large-scale application；With Fossil fuel reformation hydrogen production
Hydrogen production efficiency is the highest, and produces CO therewith2、CO、SO2Pollute environment etc. harmful gas, do not meet the theory of Green Development.Storage
Deposit aspect, not yet find effective storing mode；As used storage Gaseous Hydrogen, bulky and energy density is low；As used storage
Hiding liquified hydrogen, then require ultralow temperature or supertension, storage tank manufacturing cost is high, and hydrogen container itself is heavy, even if filling in hydrogen container
Man Qing, stores hydrogen amount and only accounts for the 5～7% of hydrogen container quality.In terms of hydrogen transport, although hydrogen has the most potential fortune
Defeated property, but it easily leaks, and even if vacuum-packed fuel tank, every day, slip still reached 2%.Therefore, dissolve the problems referred to above,
One of approach realizing the utilization of Hydrogen Energy effective and safe realizes instant hydrogen manufacturing exactly.
Energy-conservation is the focus that automobile industry development is planned with new-energy automobile.In the face of the energy shape that global range is increasingly serious
Gesture and environmental protection pressure, in recent years, World Main Auto produce state all using development new-energy automobile as improve inter-industry competition ability,
Keep the vital measure of Sustainable Socioeconomic Development.Calendar year 2001, China has formulated the science and technology of national energy-saving and new-energy automobile
Developing goal, plan is the time with 6～8 years, completes the industrialization of LEV.Hydrogen is to realize as the energy of automobile
The master of the energy-conservation science and technology object with new-energy automobile of China one of arranges, but before vehicle-mounted hydrogen production technology does not break through, vapour
Car only uses and stores hydrogen and using Hydrogen Energy as the energy of automobile, and storage hydrogen could be used must to increase automobile weight as energy source of car
Amount, contradicts with current automotive light weight technology developing direction.Therefore, use relatively inexpensive controlled hydrogen manufacturing mode, hydrogen manufacturing at any time,
Using at any time, this is also to realize hydrogen cell automobile extensively to apply the problem that have to solve.
Chinese patent CN102992263A discloses a kind of Al-Bi-NaCl-alkali metal or hydride hydrolytic hydrogen production composite wood
Material；CN102910582A discloses a kind of miniature hydrogen generating system based on aluminium alloy/borohydride hydrolytic reaction and hydrogen production process；
CN104190916A discloses a kind of antioxidative hydrolytic hydrogen production composite granule and preparation method thereof；CN103879959A discloses
The aluminum-based composite hydrogen manufacturing material of a kind of high unit hydrogen output and preparation thereof and application；CN104401940A discloses a kind of aluminum and closes
The preparation method of gold/borohydride hydrogen making system；CN103861645A disclose a kind of aluminum/water react controlled catalyst for preparing hydrogen and
Its manufacture method.Although in prior art, utilized aluminium alloy hydrolytic hydrogen production technology, but the hydrogen output of alloy and hydrogen-producing speed
The highest, it is difficult to meet the requirement of hydrogen cell automobile.
Summary of the invention
It is an object of the invention to provide a kind of hydrogen output and the high hydrolytic hydrogen production aluminium alloy of hydrogen-producing speed and preparation side thereof
Method.
The invention provides the preparation method of a kind of hydrolytic hydrogen production aluminium alloy, to include that the component of following mass content is former
Material: Al 60～97wt%, Ga 0.5～10wt%, In 0.5～10wt%, Sr 0.5～10wt%, SnCl21～
10wt%, carries out ball milling and obtains hydrolytic hydrogen production aluminium alloy.
Preferably, described raw material includes the component of following mass content: Al 70～93wt%, Ga 1～8wt%, In 1
～8wt%, Sr 1～8wt%, SnCl22～8wt%.
Preferably, described raw material includes the component of following mass content: Al 85～90wt%, Ga 2～5wt%, In 2
～5wt%, Sr 2～5wt%, SnCl23～5wt%.
Preferably, described Ga is liquid.
Preferably, described ball milling is carried out under inert gas shielding.
Preferably, the ratio of grinding media to material of described ball milling is 10～25:1.
Preferably, the time of described ball milling is 1～24h.
Preferably, described ball milling is carried out in ball mill, and the speed of mainshaft of described ball mill is 300～550r/min.
Present invention also offers a kind of hydrolytic hydrogen production aluminium alloy prepared according to technique scheme, described hydrolytic hydrogen production aluminum
The particle diameter of alloy is 100～200 μm.
The present invention uses Mechanical Alloying, with include following mass content component as raw material: Al 60～
97wt%, Ga 0.5～10wt%, In 0.5～10wt%, Sr 0.5～10wt%, SnCl21～10wt%, carry out ball milling
Obtain hydrolytic hydrogen production aluminium alloy.In ma process, metal dust produce under the effect of mechanical force plastic deformation repeatedly,
Cold welding, broken etc., be mutually diffused occurring solid-state reaction between atom so that the powder surface of synthesis occur defect, should
Power increases, system free energy increases, and then improves the activity of aluminum-water reaction；Ga and In is low-melting-point metal, and Sr is active metal,
In mechanical milling process, destroy the oxide of aluminum surface compact, improve the reactivity of aluminum-water reaction；In mechanical milling process, SnCl2Make
Eliminate the agglomeration of aluminium powder for grinding aid, and metallic aluminum surface can be made to produce substantial amounts of unsalted surface and defect, improve
The hydrolytic hydrogen production performance of material.Test result indicate that, hydrolytic hydrogen production aluminium alloy prepared by the preparation method that the present invention provides is often
Temperature is lower contact with water after can direct reaction, there is no Lag time, hydrogen output up to 1210mL/g, product hydrogen rate up to
97.3%, real-time hydrogen manufacturing and real-time hydrogen supply can be reached, it is adaptable to provide high-purity hydrogen source for hydrogen-oxygen fuel cell automobile.
The preparation method that the present invention provides reduces the consumption of precious metal element, and with low cost, technique is simple, it is adaptable to work
Industry metaplasia is produced.
Detailed description of the invention
The invention provides the preparation method of a kind of hydrolytic hydrogen production aluminium alloy, to include that the component of following mass content is former
Material: Al 60～97wt%, Ga 0.5～10wt%, In 0.5～10wt%, Sr 0.5～10wt%, SnCl21～
10wt%, carries out ball milling and obtains hydrolytic hydrogen production aluminium alloy.
In the present invention, described raw material includes the Al that mass content is 60～97wt%, and preferably 70～93wt% are more excellent
Elect 85～90wt% as.In the present invention, the purity of described Al is preferably not lower than 99%.In the present invention, described Al is preferred
For Al powder；Described Al powder is preferably dimensioned to be 100～200 mesh, more preferably 140～160 mesh.In the present invention, described Al warp
React generation hydrogen with water after activation.
In the present invention, described raw material includes the Ga that mass content is 0.5～10wt%, and preferably 1～8wt% are more excellent
Elect 2～5wt% as.In the present invention, the purity of described Ga is preferably not lower than 99.9%.In the present invention, described Ga is preferred
For liquid.In the present invention, described Ga dissolves Al in mechanical milling process, makes the Al surface being dissolved in Ga cannot form oxidation
Film, improves the hydrolytic hydrogen production performance of aluminium alloy.
In the present invention, described raw material includes the In that mass content is 0.5～10wt%, and preferably 1～8wt% are more excellent
Elect 2～5wt% as.In the present invention, the purity of described In is preferably not lower than 99.9%.In the present invention, described In is preferred
For In powder；Described In powder is preferably dimensioned to be 100～200 mesh, more preferably 140～160 mesh.In the present invention, described In is
Low-melting-point metal, destroys the oxide of aluminum surface compact in mechanical milling process, improves the reactivity of aluminum-water reaction.
In the present invention, described raw material includes the Sr that mass content is 0.5～10wt%, and preferably 1～8wt% are more excellent
Elect 2～5wt% as.In the present invention, the purity of described Sr is preferably not lower than 99.99%.In the present invention, described Sr is preferred
For Sr powder；Described Sr powder is preferably dimensioned to be 100～200 mesh, more preferably 140～160 mesh.In the present invention, described Sr is
Active metal, makes the dense oxidation film on aluminum surface become island shape in mechanical milling process, destroys the company of original dense oxidation film
Continuous property.
In the present invention, described raw material includes the SnCl that mass content is 1～10wt%2, preferably 2～8wt%, more excellent
Elect 3～5wt% as.In the present invention, described SnCl2Purity be preferably not lower than 99%.In the present invention, described SnCl2Excellent
Elect powder as；The particle diameter of described powder is preferably 50～100 mesh.In the present invention, described SnCl2Aluminium powder is eliminated as grinding aid
Agglomeration, and metallic aluminum surface can be made to produce substantial amounts of unsalted surface and defect, improve the hydrolytic hydrogen production of material
Energy.
The present invention carries out ball milling after raw material mixing described in technique scheme, obtains hydrolytic hydrogen production aluminium alloy.At this
In bright, described ball milling is preferably carried out under inert gas shielding.In the present invention, the ratio of grinding media to material of described ball milling be preferably 10～
25:1, more preferably 12～20:1, most preferably 14～16:1；The time of described ball milling be preferably 1～24h, more preferably 5～
20h, most preferably 10～15h.
In the present invention, described ball milling is preferably carried out in ball mill.In the present invention, the speed of mainshaft of described ball mill
Preferably 300～550r/min, more preferably 350～450r/min, most preferably 380～420r/min.
The present invention does not has special restriction to the kind of described ball mill, uses ball mill well known to those skilled in the art
?.In the present invention, during described ball mill is preferably planetary ball mill, stirring ball mill and vibrator
Kind, more preferably planetary ball mill.In an embodiment of the present invention, described ball mill can be specially the planetary ball of QM-3SP2
Grinding machine.
The present invention does not has special restriction to the ball grinder of described ball mill and the material of abrading-ball, uses people in the art
The material of the ball milling alloy known to Yuan.In the present invention, the material of described ball grinder and abrading-ball is preferably all rustless steel, oxygen
Change aluminum pottery or Achates, more preferably aluminium oxide ceramics.
Hydrolytic hydrogen production aluminum alloy surface for obtaining after preventing ball milling is oxidized, the present invention preferably after ball milling completes by institute
State the hydrolytic hydrogen production aluminium alloy that ball milling obtains and carry out vacuum or inert gas shielding.
Present invention also offers hydrolytic hydrogen production aluminium alloy prepared by preparation method described in a kind of technique scheme, described water
The particle diameter solving hydrogen manufacturing aluminium alloy is 100～200 μm, preferably 120～150 μm.
In order to further illustrate the present invention, the hydrolytic hydrogen production aluminium alloy present invention provided below in conjunction with embodiment and system thereof
Preparation Method is described in detail, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1:
With the Al powder that 100 mesh purity are more than 99% of 89wt%, liquid Ga that purity is more than 99.9% of 2wt%,
The In powder that 100 mesh purity are more than 99.9% of 2wt%, the Sr powder that 100 mesh purity are more than 99.99% of 3wt%, 4wt%
Particle diameter be 50 mesh purity be the SnCl of more than 99%2For raw material, in the glove box of full argon, raw material and abrading-ball are placed in
Sealing in ball grinder, ratio of grinding media to material is that the material of 25:1, ball grinder and abrading-ball is aluminium oxide ceramics, at the planetary ball of QM-3SP2
With the rotating speed ball milling 24h of 550r/min in grinding machine, obtain the hydrolytic hydrogen production Al alloy powder that particle diameter is 200 μm.
The hydrolytic hydrogen production Al alloy powder obtained and 25 DEG C of water mixing are carried out hydrolysis, tests hydrolytic hydrogen production performance.
This hydrolytic hydrogen production Al alloy powder occurs immediately upon vigorous reaction after contacting with water, and hydrolytic hydrogen production the performance test results is as shown in table 1.
Embodiment 2:
With the Al powder that 150 mesh purity are more than 99% of 86wt%, liquid Ga that purity is more than 99.9% of 2wt%,
The In powder that 150 mesh purity are more than 99.9% of 3wt%, the Sr powder that 150 mesh purity are more than 99.99% of 4wt%, 5wt%
Particle diameter be 100 mesh purity be the SnCl of more than 99%2For raw material, in the glove box of full argon, raw material and abrading-ball are placed in
Sealing in ball grinder, ratio of grinding media to material is that the material of 15:1, ball grinder and abrading-ball is aluminium oxide ceramics, at the planetary ball of QM-3SP2
With the rotating speed ball milling 20h of 500r/min in grinding machine, obtain the hydrolytic hydrogen production Al alloy powder that particle diameter is 100 μm.
The hydrolytic hydrogen production Al alloy powder obtained and 25 DEG C of water mixing are carried out hydrolysis, tests hydrolytic hydrogen production performance.
This hydrolytic hydrogen production Al alloy powder occurs immediately upon vigorous reaction after contacting with water, and hydrolytic hydrogen production the performance test results is as shown in table 1.
Embodiment 3:
With the Al powder that 200 mesh purity are more than 99% of 88wt%, liquid Ga that purity is more than 99.9% of 3wt%,
The In powder that 200 mesh purity are more than 99.9% of 2wt%, the Sr powder that 200 mesh purity are more than 99.99% of 3wt%, 4wt%
Particle diameter be 100 mesh purity be the SnCl of more than 99%2For raw material, in the glove box of full argon, raw material and abrading-ball are placed in
Sealing in ball grinder, ratio of grinding media to material is that the material of 20:1, ball grinder and abrading-ball is aluminium oxide ceramics, at the planetary ball of QM-3SP2
With the rotating speed ball milling 6h of 360r/min in grinding machine, obtain the hydrolytic hydrogen production Al alloy powder that particle diameter is 150 μm.
The hydrolytic hydrogen production Al alloy powder obtained and 25 DEG C of water mixing are carried out hydrolysis, tests hydrolytic hydrogen production performance.
This hydrolytic hydrogen production Al alloy powder occurs immediately upon vigorous reaction after contacting with water, and hydrolytic hydrogen production the performance test results is as shown in table 1.
Embodiment 4:
With the Al powder that 180 mesh purity are more than 99% of 85wt%, liquid Ga that purity is more than 99.9% of 3wt%,
The In powder that 180 mesh purity are more than 99.9% of 3wt%, the Sr powder that 150 mesh purity are more than 99.99% of 4wt%, 5wt%
Particle diameter be 50 mesh purity be the SnCl of more than 99%2For raw material, in the glove box of full argon, raw material and abrading-ball are placed in
Sealing in ball grinder, ratio of grinding media to material is that the material of 10:1, ball grinder and abrading-ball is aluminium oxide ceramics, at the planetary ball of QM-3SP2
With the rotating speed ball milling 2h of 400r/min in grinding machine, obtain the hydrolytic hydrogen production Al alloy powder that particle diameter is 180 μm.
The hydrolytic hydrogen production Al alloy powder obtained and 25 DEG C of water mixing are carried out hydrolysis, tests hydrolytic hydrogen production performance.
This hydrolytic hydrogen production Al alloy powder occurs immediately upon vigorous reaction after contacting with water, and hydrolytic hydrogen production the performance test results is as shown in table 1.
Table 1 embodiment of the present invention hydrolytic hydrogen production aluminium alloy hydrogen manufacturing performance
As can be seen from the above embodiments, the hydrolytic hydrogen production aluminium alloy that the present invention provides can immediate response in the water of 25 DEG C
Producing hydrogen, do not have Lag time, final hydrogen output is up to 1220mL/g, and finally product hydrogen rate is up to 98.1%, Ke Yida
To real-time hydrogen manufacturing and real-time hydrogen supply.
The above is only the preferred embodiment of the present invention, and the present invention not makees any pro forma restriction.Should
Point out, for those skilled in the art, under the premise without departing from the principles of the invention, it is also possible to if making
Dry improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (9)
1. a preparation method for hydrolytic hydrogen production aluminium alloy, with include following mass content component as raw material: Al 60～
97wt%, Ga 0.5～10wt%, In 0.5～10wt%, Sr 0.5～10wt%, SnCl21～10wt%, carry out ball milling
Obtain hydrolytic hydrogen production aluminium alloy.
Preparation method the most according to claim 1, it is characterised in that described raw material includes the component of following mass content:
Al 70～93wt%, Ga 1～8wt%, In 1～8wt%, Sr 1～8wt%, SnCl22～8wt%.
Preparation method the most according to claim 2, it is characterised in that described raw material includes the component of following mass content:
Al 85～90wt%, Ga 2～5wt%, In 2～5wt%, Sr 2～5wt%, SnCl23～5wt%.
4. according to the preparation method described in claims 1 to 3 any one, it is characterised in that described Ga is liquid.
Preparation method the most according to claim 1, it is characterised in that described ball milling is carried out under inert gas shielding.
Preparation method the most according to claim 5, it is characterised in that the ratio of grinding media to material of described ball milling is 10～25:1.
7. according to the preparation method described in claim 5 or 6, it is characterised in that the time of described ball milling is 1～24h.
Preparation method the most according to claim 7, it is characterised in that described ball milling is carried out in ball mill, described ball milling
The speed of mainshaft of machine is 300～550r/min.
9. the hydrolytic hydrogen production aluminium alloy that in claim 1～8 prepared by preparation method described in any one, particle diameter be 100～
200μm。
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Cited By (2)
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| CN110155943A (en) * | 2019-05-13 | 2019-08-23 | 湖北工业大学 | Super-active hydrolytic hydrogen production aluminum matrix composite and preparation method thereof |
| CN111807322A (en) * | 2019-04-10 | 2020-10-23 | 吉林省氢汇新能源有限公司 | Method for preparing hydrogen and coproducing pseudo-boehmite and/or aluminum oxide by aluminum water reaction |
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| CN110155943A (en) * | 2019-05-13 | 2019-08-23 | 湖北工业大学 | Super-active hydrolytic hydrogen production aluminum matrix composite and preparation method thereof |
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| CN106191541B (en) | 2017-12-12 |
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