CN106241733B - A kind of composite for hydrogen storage preparation method of magnesium metal and soluble starch pyrogen - Google Patents
A kind of composite for hydrogen storage preparation method of magnesium metal and soluble starch pyrogen Download PDFInfo
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- CN106241733B CN106241733B CN201610587591.6A CN201610587591A CN106241733B CN 106241733 B CN106241733 B CN 106241733B CN 201610587591 A CN201610587591 A CN 201610587591A CN 106241733 B CN106241733 B CN 106241733B
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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
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0026—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof of one single metal or a rare earth metal; Treatment thereof
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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
- Y02E60/32—Hydrogen storage
Abstract
A kind of composite for hydrogen storage preparation method of magnesium metal and soluble starch pyrogen; soluble starch is mainly placed in tube furnace by it; in the case where flowing hydrogen-argon-mixed body protection, 500 DEG C and constant temperature 12h are warming up to, soluble starch thermal decomposition product (PSS) additive is made;PSS is mixed with metal magnesium powder according to 1: 35 mass ratio, is placed in containing in 4MPa hydrogen tubular reactors, is handled 20 30h, carry out ball-milling treatment after cooling, obtain Mg PSS composite for hydrogen storage.Present invention process is simple, raw material is easy to get, cost is cheap, and the composite for hydrogen storage of preparation has good suction/hydrogen discharging performance, suitable for industrialized production.
Description
Technical field:
The invention belongs to field of functional materials, more particularly to a kind of composite for hydrogen storage and preparation method thereof.
Background technology:
The development of science and technology be unable to do without energy resource consumption, and the use of traditional fossil energy can bring serious environmental pollution again
Problem, therefore, the R and D of clean energy resource are extremely urgent.Hydrogen Energy as a kind of novel energy, have it is environment-friendly,
The features such as energy storage is high, reserves are big and receive extensive concern, but be present very hang-up in storage due to it and transport, greatly limit
The application of its actual aspect is made.Research for many years find magnesium-base hydrogen storage material have theoretical hydrogen storage content high (7.6wt.%),
Raw material is easy to get and the features such as good cycling stability, it is considered to be the hydrogen storage material most possibly applied, but its hydrogen discharging temperature
Higher (350 DEG C), significantly limit its application in practice.
The method for improving magnesium-base hydrogen storage material performance at present mainly has two kinds, and one kind is by magnesium metal and other materials alloy
Change, it is another then be introducing additive and form composite.Chinese invention patent 03149653.9 discloses one kind and uses hydrogen
The method that change method prepares magnesium base alloy hydrogen storage material.The hydrogen storage material of acquisition is greatly improved on hydrogen discharging temperature is inhaled, but makes
Standby absorption hydrogen amount is too low, it is impossible to meets actual application.Chinese invention patent 201310224596.9 then discloses one kind
Mg-based composite hydrogen storage material and preparation method thereof.The patent is after using plasmaassisted ball milling, gained Mg/MgF2It is compound
The hydrogen discharging performance of hydrogen storage material is greatly improved, but extra gas ions auxiliary body, cost are needed to use in manufacture craft
It is of a relatively high.
The content of the invention:
It is an object of the invention to provide a kind of technique it is simple, be easy to apply, magnesium metal that hydrogen storage property is good with can
The composite for hydrogen storage preparation method of soluble starch pyrogen.The present invention mainly uses soluble starch thermal decomposition product (PSS)
For additive, new Mg-base hydrogen-bearing composite is prepared with metal magnesium powder hydrogenation.
The preparation method of the present invention is as follows:
(1) soluble starch is placed in tube furnace, under the hydrogen-argon-mixed body flowing atmosphere protection containing 10% hydrogen,
500 DEG C, and isothermal pyrolysis processing 12h are warming up to 5 DEG C/min heating rate, after naturally cooling to room temperature, that is, obtained solvable
Property starch thermal decomposition product (PSS) additive;
(2) by PSS and metal magnesium powder according to 1:3~5 ratio is well mixed, and is subsequently placed in tubular reactor,
In the atmosphere of 4MPa hydrogen, with 5~10 DEG C/min heating rate by room temperature to 400 DEG C, and constant temperature handles 20~30h,
Hydrogenated products are taken out after naturally cooling to room temperature;
(3) under argon gas protection, it is 10 that the hydrogenated products of step (2), which are placed in ball grinder, and carry out ball-milling treatment ratio of grinding media to material
~40:1, rotating speed is 300~500r/min, using batch (-type) ball-milling treatment, per ball milling 30min, interval 15min, and, during ball milling
Between be 1~5h, ball milling naturally cools to room temperature after terminating, argon gas protection under packed, obtain Mg-PSS hydrogen storages and answer
Condensation material.
The present invention has advantages below compared with prior art:
1st, the Mg-PSS composite hydrogen storage material hydrogen storage properties prepared are good, at 200 DEG C, can inhale hydrogen in 3500s
5.53Wt.%, at 350 DEG C, hydrogen 5.12Wt.% can be put in 1000s.
2nd, cost is cheap, and the metal Mg powder and soluble starch raw material used is easy to get.
3rd, preparation technology is simple, easily operated, it is easy to accomplish Industry Promotion.
Brief description of the drawings:
Fig. 1 is the composite hydrogen storage material and suction after the ball milling of the embodiment of the present invention 1/put the XRD diffraction patterns after hydrogen, and (a) is
The later XRD diffraction patterns of ball milling, (b) are that to put XRD diffraction patterns, (c) of the composite hydrogen storage material after hydrogen be the compound storage after suction hydrogen
The XRD diffraction patterns of hydrogen material.
Fig. 2 is that Mg-PSS composite hydrogen storage materials prepared by the embodiment of the present invention 1 are depressed in 423K, 3MPa hydrogen, with pure Mg powder
Hydrogen-absorption speed comparison diagram.
Fig. 3 is that Mg-PSS composite hydrogen storage materials prepared by the embodiment of the present invention 2 are depressed in 473K, 3MPa hydrogen, with pure Mg powder
Hydrogen-absorption speed comparison diagram.
Fig. 4 is that Mg-PSS composite hydrogen storage materials prepared by the embodiment of the present invention 3 are depressed in 573K, 0.01MPa hydrogen, with pure Mg
The hydrogen discharging rate comparison diagram of powder.
Fig. 5 is that Mg-PSS composite hydrogen storage materials prepared by the embodiment of the present invention 4 are depressed in 623K, 0.01MPa hydrogen, with pure Mg
The hydrogen discharging rate comparison diagram of powder.
Embodiment:
Embodiment 1
Soluble starch is placed in tube furnace, under the hydrogen-argon-mixed body flowing atmosphere protection containing 10% hydrogen, with 5
DEG C/min heating rate is warming up to 500 DEG C, and isothermal pyrolysis processing 12h, after naturally cooling to room temperature, that is, obtain soluble form sediment
Powder thermal decomposition product (PSS) additive;By PSS additives and metal magnesium powder in mass ratio 1:It is placed in and contains after 5 ratio uniform mixing
In the tubular reactor for having 4.0MPa high-purity hydrogens (99.99%) atmosphere, with 5 DEG C/min heating rate by room temperature extremely
400 DEG C, and constant temperature handles 30h, is transferred to after natural cooling in ball grinder, carries out ball milling using planetary ball mill, ball matter is
Stainless steel, ball material mass ratio are 30:1, rotating speed 300r/min, the high-purity argon gas for being filled with 0.1MPa carries out ball milling, per ball milling 30
Min, interval 15min, Ball-milling Time 5h, treat to naturally cool to room temperature after ball milling, take out and carry out under argon gas protection
Pack, obtain Mg-PSS composite for hydrogen storage.
As shown in Figure 1, it can be seen that suction hydrogen is carried out to composite for hydrogen storage and is handled, the magnesium metal in composite for hydrogen storage
Metal magnesium hydride MgH can be changed into2, put metal magnesium hydride MgH after hydrogen2Then it is fully converted to metal Mg.
Hydrogen sucking function is tested:
Take the composite for hydrogen storage of the above-mentioned preparations of 0.9g to load P-C-T testers and carry out 423K rate tests, test result
As shown in Figure 2.The composite inhales hydrogen speed 10 times of Mg powder under the conditions of 500s or so hydrogen-sucking amount is same treatment
Rate and last hydrogen-sucking amount are obviously improved.
Embodiment 2
Soluble starch is placed in tube furnace, under the hydrogen-argon-mixed body flowing atmosphere protection containing 10% hydrogen, with 5
DEG C/min heating rate is warming up to 500 DEG C, and isothermal pyrolysis processing 12h, after naturally cooling to room temperature, that is, obtain soluble form sediment
Powder thermal decomposition product (PSS) additive;By PSS additives and metal magnesium powder in mass ratio 1:It is placed in and contains after 4 ratio uniform mixing
In the tubular reactor for having 4.0MPa high-purity hydrogens (99.99%) atmosphere, with 7 DEG C/min heating rate by room temperature extremely
400 DEG C, and constant temperature handles 25h, is transferred to after natural cooling in ball grinder, carries out ball milling using planetary ball mill, ball matter is
Stainless steel, ball material mass ratio are 40:1, rotating speed 300r/min, the high-purity argon gas for being filled with 0.1MPa carries out ball milling, per ball milling
30min, interval 15min, Ball-milling Time 4h, treat to naturally cool to room temperature after ball milling, take out and go forward side by side under argon gas protection
Row packs, and obtains Mg-PSS composite for hydrogen storage.
Hydrogen sucking function is tested:
Take the composite for hydrogen storage of the above-mentioned preparations of 0.9g to load P-C-T testers and carry out 473K rate tests, test result
As shown in Figure 3.The hydrogen-absorption speed of the composite hydrogen storage material will be substantially better than the Mg powder of same treatment method, moreover, inhale hydrogen
When amount reaches 2wt.%, composite hydrogen storage material only needs 370s, and the Mg powder of same treatment condition does not all reach then in 4000s.
Embodiment 3
Soluble starch is placed in tube furnace, under the hydrogen-argon-mixed body flowing atmosphere protection containing 10% hydrogen, with 5
DEG C/min heating rate is warming up to 500 DEG C, and isothermal pyrolysis processing 12h, after naturally cooling to room temperature, that is, obtain soluble form sediment
Powder thermal decomposition product (PSS) additive;By PSS additives and metal magnesium powder in mass ratio 1:It is placed in and contains after 3 ratio uniform mixing
In the tubular reactor for having 4.0MPa high-purity hydrogens (99.99%) atmosphere, with 10 DEG C/min heating rate by room temperature extremely
400 DEG C, and constant temperature handles 20h, is transferred to after natural cooling in ball grinder, carries out ball milling using planetary ball mill, ball matter is
Stainless steel, ball material mass ratio are 20:1, rotating speed 400r/min, the high-purity argon gas for being filled with 0.1MPa carries out ball milling, per ball milling
30min, interval 15min, Ball-milling Time 2h, treat to naturally cool to room temperature after ball milling, take out and go forward side by side under argon gas protection
Row packs, and obtains Mg-PSS composite for hydrogen storage.
Hydrogen discharging performance is tested:
Take the composite for hydrogen storage of the above-mentioned preparations of 0.9g to load P-C-T testers and carry out 573K rate tests, give during heating
3.0MPa hydrogen pressure is given to put hydrogen in temperature-rise period to suppress sample, test result is as shown in Fig. 4.The composite hydrogen storage material
Hydrogen desorption capacity and hydrogen discharging rate have very big lifting, in 2000s, the hydrogen desorption capacity of Mg-PSS composite hydrogen storage materials is
1.83wt.%, and the Mg powder under the same terms is only 0.11 wt.%.
Embodiment 4
Soluble starch is placed in tube furnace, under the hydrogen-argon-mixed body flowing atmosphere protection containing 10% hydrogen, with 5
DEG C/min heating rate is warming up to 500 DEG C, and isothermal pyrolysis processing 12h, after naturally cooling to room temperature, that is, obtain soluble form sediment
Powder thermal decomposition product (PSS) additive;By PSS additives and metal magnesium powder in mass ratio 1:It is placed in and contains after 5 ratio uniform mixing
In the tubular reactor for having 4.0MPa high-purity hydrogens (99.99%) atmosphere, with 8 DEG C/min heating rate by room temperature extremely
400 DEG C, and constant temperature handles 30h, is transferred to after natural cooling in ball grinder, carries out ball milling using planetary ball mill, ball matter is
Stainless steel, ball material mass ratio are 10:1, rotating speed 500r/min, the high-purity argon gas for being filled with 0.1MPa carries out ball milling, per ball milling
30min, interval 15min, Ball-milling Time 1h, treat to naturally cool to room temperature after ball milling, take out and go forward side by side under argon gas protection
Row packs, and obtains Mg-PSS composite for hydrogen storage.
Hydrogen discharging performance is tested:
Take the composite for hydrogen storage of the above-mentioned preparations of 0.9g to load P-C-T testers and carry out 623K rate tests, give during heating
3.0MPa hydrogen pressure is given to put hydrogen in temperature-rise period to suppress sample, test result is as shown in Fig. 5.The composite hydrogen storage material
Hydrogen desorption capacity and hydrogen discharging rate have a very big lifting, Mg-PSS composite hydrogen storage materials are just almost put hydrogen in 500s or so and put down
Platform, and pure Mg puts hydrogen unobvious under the same terms.Moreover, composite maximum hydrogen desorption capacity at this temperature is much higher than Mg
Powder.
Claims (1)
- A kind of 1. composite for hydrogen storage preparation method of magnesium metal and soluble starch pyrogen, it is characterised in that:Its preparation side Method is as follows:(1) soluble starch is placed under the hydrogen-argon-mixed body flowing atmosphere protection containing 10% hydrogen, with 5 DEG C/min heating Speed is warming up to 500 DEG C, and isothermal pyrolysis processing 12h, after naturally cooling to room temperature, that is, obtains soluble starch thermal decomposition product (PSS) additive;(2) by PSS and metal magnesium powder according to 1:3~5 ratio is well mixed, and is subsequently placed in tubular reactor, in 4MPa hydrogen In the atmosphere of gas, with 5~10 DEG C/min heating rate by room temperature to 400 DEG C, and constant temperature handles 20~30h, naturally cold But to taking out hydrogenated products after room temperature;(3) under argon gas protection, the hydrogenated products of step (2) are placed in ball grinder carry out ball-milling treatment ratio of grinding media to material be 10~ 40:1, rotating speed is 300~500r/min, using batch (-type) ball-milling treatment, every ball milling 30min, interval 15min, and, Ball-milling Time For 1~5h, ball milling naturally cools to room temperature after terminating, and is packed under argon gas protection, it is compound to obtain Mg-PSS hydrogen storages Material.
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101549854A (en) * | 2009-05-13 | 2009-10-07 | 安徽工业大学 | Mg-based composite hydrogen storage material containing alkaline earth metals-aluminum hydride and preparation method thereof |
CN104909337A (en) * | 2015-07-03 | 2015-09-16 | 燕山大学 | Lithium metaborate hydrogen storage composite material adulterated with lithium hydride and preparation method thereof |
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KR100924471B1 (en) * | 2007-11-01 | 2009-11-03 | 한국에너지기술연구원 | Production of aluminum hydride type hydrogen storage material by mechnochemical method |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN101549854A (en) * | 2009-05-13 | 2009-10-07 | 安徽工业大学 | Mg-based composite hydrogen storage material containing alkaline earth metals-aluminum hydride and preparation method thereof |
CN104909337A (en) * | 2015-07-03 | 2015-09-16 | 燕山大学 | Lithium metaborate hydrogen storage composite material adulterated with lithium hydride and preparation method thereof |
Non-Patent Citations (1)
Title |
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烟煤粘结纳米镁基储氢材料的制备及吸放氢性能;张同环等;《功能材料》;20131231;第44卷(第20期);第3045-3048页 * |
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