CN106241733A - A kind of magnesium metal and the composite for hydrogen storage preparation method of soluble starch pyrogen - Google Patents
A kind of magnesium metal and the composite for hydrogen storage preparation method of soluble starch pyrogen Download PDFInfo
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- CN106241733A CN106241733A CN201610587591.6A CN201610587591A CN106241733A CN 106241733 A CN106241733 A CN 106241733A CN 201610587591 A CN201610587591 A CN 201610587591A CN 106241733 A CN106241733 A CN 106241733A
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- hydrogen
- composite
- hydrogen storage
- pss
- soluble starch
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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 magnesium metal and the composite for hydrogen storage preparation method of soluble starch pyrogen; soluble starch is mainly placed in tube furnace by it; under hydrogen-argon-mixed body protection of flowing, it is warming up to 500 DEG C and constant temperature 12h, prepares soluble starch thermal decomposition product (PSS) additive;PSS is mixed according to the mass ratio of 1: 35 with metal magnesium powder, is placed in containing in 4MPa hydrogen tubular reactor, processes 20 30h, after cooling, carry out ball-milling treatment, obtain Mg PSS composite for hydrogen storage.Present invention process is simple, raw material is easy to get, with low cost, the composite for hydrogen storage of preparation has good suction/hydrogen discharging performance, it is adaptable to industrialized production.
Description
Technical field:
The invention belongs to field of functional materials, 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 again serious environmental pollution
Problem, therefore, the R and D of clean energy resource are extremely the most urgent.Hydrogen Energy as a kind of novel energy, have environmental friendliness,
The features such as energy storage is high, reserves are big and receive extensive concern, but owing to its storage and transport exist very hang-up, greatly limit
Make the application of its actual aspect.Research for many years find magnesium-base hydrogen storage material have theoretical hydrogen storage content height (7.6wt.%),
Raw material is easy to get and the feature such as good cycling stability is it is considered to be the hydrogen storage material of most possible application, but its hydrogen discharging temperature
Higher (350 DEG C), significantly limit its application in practice.
The method improving magnesium-base hydrogen storage material performance at present mainly has two kinds, and one is by magnesium metal and other materials alloy
Changing, another kind is then introduced into additive and forms composite.Chinese invention patent 03149653.9 discloses a kind of use hydrogen
Change method prepares the method for magnesium base alloy hydrogen storage material.The hydrogen storage material obtained is greatly improved on suction hydrogen discharging temperature, but system
Standby absorption hydrogen amount is too low, it is impossible to meet actual application.Chinese invention patent 201310224596.9 then discloses one
Mg-based composite hydrogen storage material and preparation method thereof.This patent is using after plasmaassisted ball milling, gained Mg/MgF2Compound
The hydrogen discharging performance of hydrogen storage material is greatly improved, but needs in processing technology to use extra gas ions auxiliary body, and cost is also
Of a relatively high.
Summary of the invention:
It is an object of the invention to provide that a kind of technique is simple, be prone to application, 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, prepare Novel magnesium base hydrogen storage composite with metal magnesium powder hydrogenation.
The preparation method of the present invention is as follows:
(1) soluble starch is placed in tube furnace, flows under atmosphere protection at the hydrogen-argon-mixed body containing 10% hydrogen,
It is warming up to 500 DEG C with the heating rate of 5 DEG C/min, and isothermal pyrolysis processes 12h, after naturally cooling to room temperature, i.e. obtains solvable
Property starch thermal decomposition product (PSS) additive;
(2) PSS is mixed homogeneously according to the ratio of 1:3~5 with metal magnesium powder, be subsequently placed in tubular reactor,
In the atmosphere of 4MPa hydrogen, with the heating rate of 5~10 DEG C/min by room temperature to 400 DEG C, and constant temperature processes 20~30h,
Hydrogenated products is taken out after naturally cooling to room temperature;
(3) under argon shield, the hydrogenated products of step (2) is placed in ball grinder that to carry out ball-milling treatment ratio of grinding media to material be 10
~40:1, rotating speed is 300~500r/min, uses batch (-type) football fan to process, every ball milling 30min, intermittently 15min, Ball-milling Time
Being 1~5h, ball milling naturally cools to room temperature after terminating, and packs under argon shield, obtains Mg-PSS hydrogen storage and is combined
Material.
The present invention compared with prior art has the advantage that
1, the Mg-PSS composite hydrogen storage material hydrogen storage property of preparation is good, at 200 DEG C, it is possible to inhale hydrogen at 3500s
5.53Wt.%, at 350 DEG C, can put hydrogen 5.12Wt.% at 1000s.
2, with low cost, the metal Mg powder of use and soluble starch raw material are easy to get.
3, preparation technology is simple, it is easy to operation, it is easy to accomplish Industry Promotion.
Accompanying drawing illustrates:
Fig. 1 is the XRD diffraction pattern after this composite hydrogen storage material and suction after the embodiment of the present invention 1 ball milling/put hydrogen, and (a) is
The later XRD diffraction pattern of ball milling, (b) be put hydrogen after the XRD diffraction pattern of this composite hydrogen storage material, (c) for inhaling this compound storage after hydrogen
The XRD diffraction pattern of hydrogen material.
Fig. 2 be the embodiment of the present invention 1 preparation Mg-PSS composite hydrogen storage material under 423K, 3MPa hydrogen pressure, with pure Mg powder
Hydrogen-absorption speed comparison diagram.
Fig. 3 be the embodiment of the present invention 2 preparation Mg-PSS composite hydrogen storage material under 473K, 3MPa hydrogen pressure, with pure Mg powder
Hydrogen-absorption speed comparison diagram.
Fig. 4 be the embodiment of the present invention 3 preparation Mg-PSS composite hydrogen storage material under 573K, 0.01MPa hydrogen pressure, with pure Mg
The hydrogen discharging rate comparison diagram of powder.
Fig. 5 be the embodiment of the present invention 4 preparation Mg-PSS composite hydrogen storage material under 623K, 0.01MPa hydrogen pressure, with pure Mg
The hydrogen discharging rate comparison diagram of powder.
Detailed description of the invention:
Embodiment 1
Soluble starch is placed in tube furnace, flows under atmosphere protection at the hydrogen-argon-mixed body containing 10% hydrogen, with 5
DEG C/heating rate of min is warming up to 500 DEG C, and isothermal pyrolysis processes 12h, after naturally cooling to room temperature, i.e. obtains solubility and forms sediment
Powder thermal decomposition product (PSS) additive;Mix to be placed on by the ratio uniform of PSS additive with metal magnesium powder 1:5 in mass ratio and contain
Have in the tubular reactor of 4.0MPa high-purity hydrogen (99.99%) atmosphere, with the heating rate of 5 DEG C/min by room temperature extremely
400 DEG C, and constant temperature process 30h, be transferred to after natural cooling in ball grinder, use planetary ball mill to carry out ball milling, and ball matter is
Rustless steel, ball material mass ratio is 30:1, and rotating speed is 300r/min, and the high-purity argon gas being filled with 0.1MPa carries out ball milling, every ball milling
30min, intermittently 15min, Ball-milling Time is 5h, naturally cools to room temperature after treating ball milling, takes out and go forward side by side under argon shield
Row packs, and obtains Mg-PSS composite for hydrogen storage.
As shown in Figure 1, it can be seen that composite for hydrogen storage is carried out inhales hydrogen and processes, the magnesium metal in composite for hydrogen storage
Magnesium metal hydride MgH can be changed into2, put magnesium metal hydride MgH after hydrogen2Then it is fully converted to metal Mg.
Hydrogen sucking function is tested:
The composite for hydrogen storage loading P-C-T tester taking the above-mentioned preparation of 0.9g carries out 423K rate test, test result
As shown in Figure 2.This composite under the conditions of the hydrogen-sucking amount of about 500s is same treatment 10 times of Mg powder, and hydrogen-absorption speed
All it is obviously improved with last hydrogen-sucking amount.
Embodiment 2
Soluble starch is placed in tube furnace, flows under atmosphere protection at the hydrogen-argon-mixed body containing 10% hydrogen, with 5
DEG C/heating rate of min is warming up to 500 DEG C, and isothermal pyrolysis processes 12h, after naturally cooling to room temperature, i.e. obtains solubility and forms sediment
Powder thermal decomposition product (PSS) additive;Mix to be placed on by the ratio uniform of PSS additive with metal magnesium powder 1:4 in mass ratio and contain
Have in the tubular reactor of 4.0MPa high-purity hydrogen (99.99%) atmosphere, with the heating rate of 7 DEG C/min by room temperature extremely
400 DEG C, and constant temperature process 25h, be transferred to after natural cooling in ball grinder, use planetary ball mill to carry out ball milling, and ball matter is
Rustless steel, ball material mass ratio is 40:1, and rotating speed is 300r/min, and the high-purity argon gas being filled with 0.1MPa carries out ball milling, every ball milling
30min, intermittently 15min, Ball-milling Time is 4h, naturally cools to room temperature after treating ball milling, takes out and go forward side by side under argon shield
Row packs, and obtains Mg-PSS composite for hydrogen storage.
Hydrogen sucking function is tested:
The composite for hydrogen storage loading P-C-T tester taking the above-mentioned preparation of 0.9g carries out 473K rate test, test result
As shown in Figure 3.The Mg powder of hydrogen-absorption speed same treatment the to be substantially better than method of this composite hydrogen storage material, moreover, inhales hydrogen
When amount reaches 2wt.%, composite hydrogen storage material only needs 370s, and the Mg powder of same treatment condition does not then reach at 4000s.
Embodiment 3
Soluble starch is placed in tube furnace, flows under atmosphere protection at the hydrogen-argon-mixed body containing 10% hydrogen, with 5
DEG C/heating rate of min is warming up to 500 DEG C, and isothermal pyrolysis processes 12h, after naturally cooling to room temperature, i.e. obtains solubility and forms sediment
Powder thermal decomposition product (PSS) additive;Mix to be placed on by the ratio uniform of PSS additive with metal magnesium powder 1:3 in mass ratio and contain
Have in the tubular reactor of 4.0MPa high-purity hydrogen (99.99%) atmosphere, with the heating rate of 10 DEG C/min by room temperature extremely
400 DEG C, and constant temperature process 20h, be transferred to after natural cooling in ball grinder, use planetary ball mill to carry out ball milling, and ball matter is
Rustless steel, ball material mass ratio is 20:1, and rotating speed is 400r/min, and the high-purity argon gas being filled with 0.1MPa carries out ball milling, every ball milling
30min, intermittently 15min, Ball-milling Time is 2h, naturally cools to room temperature after treating ball milling, takes out and go forward side by side under argon shield
Row packs, and obtains Mg-PSS composite for hydrogen storage.
Hydrogen discharging performance is tested:
The composite for hydrogen storage loading P-C-T tester taking the above-mentioned preparation of 0.9g carries out 573K rate test, gives during intensification
Giving the hydrogen pressure of 3.0MPa to the hydrogen of putting suppressing sample in temperature-rise period, test result is as shown in Figure 4.This composite hydrogen storage material
Hydrogen desorption capacity and hydrogen discharging rate have had the biggest lifting, and when 2000s, the hydrogen desorption capacity of Mg-PSS composite hydrogen storage material is
1.83wt.%, and the Mg powder under the same terms is only 0.11wt.%.
Embodiment 4
Soluble starch is placed in tube furnace, flows under atmosphere protection at the hydrogen-argon-mixed body containing 10% hydrogen, with 5
DEG C/heating rate of min is warming up to 500 DEG C, and isothermal pyrolysis processes 12h, after naturally cooling to room temperature, i.e. obtains solubility and forms sediment
Powder thermal decomposition product (PSS) additive;Mix to be placed on by the ratio uniform of PSS additive with metal magnesium powder 1:5 in mass ratio and contain
Have in the tubular reactor of 4.0MPa high-purity hydrogen (99.99%) atmosphere, with the heating rate of 8 DEG C/min by room temperature extremely
400 DEG C, and constant temperature process 30h, be transferred to after natural cooling in ball grinder, use planetary ball mill to carry out ball milling, and ball matter is
Rustless steel, ball material mass ratio is 10:1, and rotating speed is 500r/min, and the high-purity argon gas being filled with 0.1MPa carries out ball milling, every ball milling
30min, intermittently 15min, Ball-milling Time is 1h, naturally cools to room temperature after treating ball milling, takes out and go forward side by side under argon shield
Row packs, and obtains Mg-PSS composite for hydrogen storage.
Hydrogen discharging performance is tested:
The composite for hydrogen storage loading P-C-T tester taking the above-mentioned preparation of 0.9g carries out 623K rate test, gives during intensification
Giving the hydrogen pressure of 3.0MPa to the hydrogen of putting suppressing sample in temperature-rise period, test result is as shown in Figure 5.This composite hydrogen storage material
Hydrogen desorption capacity and hydrogen discharging rate have had the biggest lifting, and it is flat that Mg-PSS composite hydrogen storage material the most almost puts hydrogen at about 500s
Platform, and under the same terms pure Mg to put hydrogen inconspicuous.Moreover, the composite maximum hydrogen desorption capacity at a temperature of being somebody's turn to do is much higher than Mg
Powder.
Claims (1)
1. a magnesium metal and the composite for hydrogen storage preparation method of 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 the intensification of 5 DEG C/min
Ramp is to 500 DEG C, and isothermal pyrolysis processes 12h, after naturally cooling to room temperature, i.e. obtains soluble starch thermal decomposition product
(PSS) additive;
(2) PSS is mixed homogeneously according to the ratio of 1:3~5 with metal magnesium powder, be subsequently placed in tubular reactor, at 4MPa hydrogen
In the atmosphere of gas, with the heating rate of 5~10 DEG C/min by room temperature to 400 DEG C, and constant temperature processes 20~30h, the coldest
But to room temperature, hydrogenated products is taken out;
(3) under argon shield, the hydrogenated products of step (2) is 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, uses batch (-type) football fan to process, every ball milling 30min, intermittently 15min, Ball-milling Time is
1~5h, ball milling naturally cools to room temperature after terminating, and packs under argon shield, obtains Mg-PSS hydrogen storage composite wood
Material.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20090044883A (en) * | 2007-11-01 | 2009-05-07 | 한국에너지기술연구원 | Production of aluminum hydride type hydrogen storage material by mechnochemical method |
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 |
-
2016
- 2016-07-25 CN CN201610587591.6A patent/CN106241733B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20090044883A (en) * | 2007-11-01 | 2009-05-07 | 한국에너지기술연구원 | Production of aluminum hydride type hydrogen storage material by mechnochemical method |
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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张同环等: "烟煤粘结纳米镁基储氢材料的制备及吸放氢性能", 《功能材料》 * |
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Effective date of registration: 20190508 Address after: 100024 Beijing Chaoyang District Jianguo Road 15 Courtyard 1 North Bank 1292 3-room Creative Life Park 8-2684 Patentee after: Zhonghua Feitian (Beijing) Enterprise Management Consulting Co., Ltd. Address before: 066004 438 west section of Hebei Avenue, Qinhuangdao, Hebei. Patentee before: Yanshan University |