CN103787273B - For the magnesium calcium base hydride powder and preparation method thereof of wide warm area hydrolytic hydrogen production - Google Patents
For the magnesium calcium base hydride powder and preparation method thereof of wide warm area hydrolytic hydrogen production Download PDFInfo
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- CN103787273B CN103787273B CN201410025998.0A CN201410025998A CN103787273B CN 103787273 B CN103787273 B CN 103787273B CN 201410025998 A CN201410025998 A CN 201410025998A CN 103787273 B CN103787273 B CN 103787273B
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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
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- 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
Abstract
Magnesium calcium base hydride powder for hydrolytic hydrogen production of the present invention, the mass percent of the component comprised and each component is: Ca
4mg
3h
1414.2 ~ 50.2%, MgH
234.8 ~ 85.7%, Mg0.1 ~ 15%, produce hydrogen rate for improving hydrolysis, be also compounded with other hydride with ∕ or salt, wherein the quality of other hydride is component Ca
4mg
3h
14, component MgH
2with 0 ~ 5% of the summation of the quality of component Mg, the quality of salt is component Ca
4mg
3h
14, component MgH
2with 0 ~ 11% of the summation of the quality of component Mg, wherein, be 0 when the content of the content of other hydride, salt is different.Above-mentioned magnesium calcium base hydride raw powder's production technology is by the postactivated suction hydrogen of the broken ball milling of magnesium calcium alloy.Magnesium calcium base hydride powder for hydrolytic hydrogen production provided by the invention, can improve hydrogen output, particularly improve the hydrogen output under room temperature and low temperature under the prerequisite ensureing reaction safety and controllability.
Description
Technical field
The invention belongs to hydrolytic hydrogen production field of material technology, particularly a kind of magnesium calcium base hydride powder for hydrolytic hydrogen production and preparation method.
Background technology
Hydrogen Energy receives much concern as a kind of clean energy and high density energy carrier, is considered to the removable energy of future ideality.First the utilization of Hydrogen Energy needs to solve hydrogen source problem, but traditional process for making hydrogen not only needs to consume a large amount of energy, and hydrogen production efficiency is relatively low.Simultaneously because hydrogen is inflammable and explosive, the security in hydrogen applications process is also a problem that must pay attention to and solve.Therefore less energy-consumption, high-level efficiency and the hydrogen storage technology of safety and stability and hydrogen production process is found significant for hydrogen utilization.
Hydrolytic hydrogen production is immediately online hydrogen source plenum system, and its restriction by the condition such as temperature, pressure is less, and theoretical hydrogen amount is higher, more can meet the requirement of current onboard hydrogen source.Current hydrolytic hydrogen production material or be that cost is high, need noble metal as catalyzer, and hydrogen manufacturing energy consumption is high, efficiency is low (as NaBH
4), or the violent security of hydrolysis reaction is low, needed for hydrogen-producing speed substantially exceeds, increase controlled difficulty, and expensive raw material price is (as LiH, NaH, LiAlH
4deng).
The people such as F.Gingl are at " Tetracalciumtrimagnesiumtetradecahydride, Ca
4mg
3h
14: thefirstternaryalkalineearthhydride " in obtained containing by Ca first
4mg
3h
14, CaH
2, MgH
2the matrix material be combined into, wherein Ca
4mg
3h
14content up to more than 90%, its objective is synthesis Ca
4mg
3h
14, its structure is described, but any research is not done to its hydrogen storage property.The contriver of present patent application is found due to Ca by research
4mg
3h
14activity is higher, and during as hydrogen storage material hydrolytic hydrogen production, reaction can be quite violent, and whole process is uncontrollable, and security is low.
Chinese patent CN101891151 discloses " a kind of magnesium-aluminum based hydride composite for hydrolytic hydrogen production ", but obtained hydride composite hydrolysis property under room temperature and low temperature is poor, and actual hydrogen-releasing rate is lower.This is because cover the Mg (OH) of unreacted composite material surface
2the Al of the beds of precipitation and Al surface compact
2o
3film hinders proceeding of reaction.And can hydrolytic hydrogen production material be hydrolyzed under room temperature even low temperature, releasing hydrogen gas concerns the scope of application and the practicality of hydrolytic hydrogen production material.
Summary of the invention
The object of the invention is to the deficiency for existing hydrogen storage material and hydrogen production process, a kind of magnesium calcium base hydride powder for hydrolytic hydrogen production is provided, to improve hydrogen output under the prerequisite ensureing reaction safety and controllability, particularly improve the hydrogen output under room temperature and low temperature.
Magnesium calcium base hydride powder for hydrolytic hydrogen production of the present invention, the mass percent of the component comprised and each component is:
Ca
4Mg
3H
1414.2～50.2%，
MgH
234.8～85.7%，
Mg0.1～15%。
Producing hydrogen rate for improving hydrolysis, above-mentioned magnesium calcium base hydride powder can be carried out ball-milling processing separately, or add other hydride with ∕ or salt on above-mentioned magnesium calcium base hydride powder basis, obtaining and be compounded with other hydride with the magnesium calcium base hydride powder of ∕ or salt.The content of other hydride described is Ca
4mg
3h
14, MgH
2with 0 ~ 5% of Mg total mass, the content of salt is Ca
4mg
3h
14, MgH
2with 0 ~ 11% of Mg total mass, wherein, be 0 when the content of the content of other hydride, salt is different.
Above-mentionedly be compounded with other hydride with in the magnesium calcium base hydride powder of ∕ or salt, other hydride described be alkalimetal hydride with ∕ or alanate, described alkalimetal hydride is that sodium hydride is with ∕ or potassium hydride KH; Described alanate is that sodium alanate is with ∕ or aluminium lithium hydride.
Above-mentionedly be compounded with other hydride with in the magnesium calcium base hydride powder of ∕ or salt, described salt is at least one in sodium-chlor, aluminum chloride, Repone K, calcium chloride, magnesium chloride, magnesium fluoride, magnesium sulfate, magnesium nitrate.
Component is Ca
4mg
3h
14, MgH
2with the magnesium calcium base hydride raw powder's production technology of Mg, processing step is as follows:
Be 10 ~ 35% by calcium mass percent, magnesium mass percent be 65 ~ 90% magnesium calcium alloy be crushed to and be less than 50 ~ 300 orders, then be (8 ~ 60) in argon gas atmosphere, ratio of grinding media to material: ball milling 0.5 ~ 5h under the condition of 1, continue after by ball milling gained magnesium calcium alloy powder 350 ~ 500 DEG C, activation 0 ~ 5 time under hydrogen pressure 3 ~ 6MPa, inhale hydrogen hydrogenation 6 ~ 24h again, obtaining component is Ca
4mg
3h
14, MgH
2with the magnesium calcium base hydride powder of Mg.
The component that aforesaid method obtains is Ca
4mg
3h
14, MgH
2not high with the product hydrogen rate that the magnesium calcium base hydride powder of Mg reacts with water under room temperature and low temperature, this is because the Mg (OH) that reaction generates
2the surface that sediment fraction covers unreacted magnesium calcium base hydride powder hinders proceeding of reaction.Producing hydrogen rate for improving hydrolysis, can be Ca by the component obtained
4mg
3h
14, MgH
2be (2 ~ 60) with the magnesium calcium base hydride powder of Mg in argon gas atmosphere, ratio of grinding media to material: ball milling 10min ~ 10h under the condition of 1.
The magnesium calcium base hydride raw powder's production technology being compounded with other hydride and ∕ or salt of the present invention, the component prepared with aforesaid method is Ca
4mg
3h
14, MgH
2with the magnesium calcium base hydride powder of Mg, other hydride with ∕ or salt are raw material, the component of content prepared by aforesaid method of other hydride described is Ca
4mg
3h
14, MgH
2with 0 ~ 5% of the magnesium calcium base hydride powder quality of Mg, the component of content prepared by aforesaid method of salt is Ca
4mg
3h
14, MgH
2with 0 ~ 11% of the magnesium calcium base hydride powder quality of Mg, wherein, the content of other hydride, the content of salt are 0 time different, and processing step is as follows: the component prepared by the aforesaid method measured is Ca
4mg
3h
14, MgH
2with the magnesium calcium base hydride powder of Mg, other hydride with ∕ or salt add in ball mill, be (2 ~ 60) in argon gas atmosphere, ratio of grinding media to material: ball milling 10min ~ 10h under the condition of 1.
Above-mentionedly be compounded with other hydride with the magnesium calcium base hydride raw powder's production technology of ∕ or salt, other hydride described are that alkalimetal hydride is with ∕ or alanate.Described alkalimetal hydride is that sodium hydride is with ∕ or potassium hydride KH; Described alanate is that sodium alanate is with ∕ or aluminium lithium hydride.
Above-mentionedly be compounded with other hydride with the magnesium calcium base hydride raw powder's production technology of ∕ or salt, described salt is at least one in sodium-chlor, aluminum chloride, Repone K, calcium chloride, magnesium chloride, magnesium fluoride, magnesium sulfate, magnesium nitrate.
Magnesium calcium base hydride powder of the present invention, can comprise water with reaction medium, inorganic salt solution (comprises NaCl, CaF
2, MgCl
2, Na
2sO
4the aqueous solution Deng salt), aqueous organopolysiloxane (comprising the aqueous solution of ethanol or ether), acidic solution (comprise citric acid or HCl, H
2sO
4, HNO
3the aqueous solution) etc. reaction produce hydrogen.
Magnesium calcium base hydride powder of the present invention, can react with water and produce hydrogen at 0 ~ 85 DEG C, can react produce hydrogen with the aqueous solution at-45 ~ 85 DEG C, adapts to warm area a wider range, also can react and produce a large amount of hydrogen under room temperature and low temperature.
Compared with prior art, the present invention has following beneficial effect:
1, magnesium calcium base hydride powder provided by the invention, due to wherein Ca
4mg
3h
14content be 14.2 ~ 50.2%, on the one hand avoid the higher Ca of reactive behavior
4mg
3h
14content too much causes hydrolysis reaction acutely uncontrollable, to ensure security.On the other hand, due to Ca
4mg
3h
14reactive behavior is higher, and reacting with reaction medium can releasing hydrogen gas fast, can break through the Mg (OH) be attached on powder granule surface in hydrogen releasing process fast
2the beds of precipitation, hinder throw out Mg (OH) to a certain extent
2in the attachment of particle surface, avoid the formation of the fine and close beds of precipitation, providing passage for continuing hydrolysis reaction, promoting the hydrolysis reaction of follow-up magnesium calcium base hydride powder, improve the actual hydrogen output of material and produce hydrogen rate.All not moisture when the theoretical hydrogen amount not carrying out compound tense magnesium calcium base hydride powder calculates up to 12.2 ~ 14.7wt%().Hydrogen output particularly under room temperature and low temperature and product hydrogen rate improve a lot, compared with CN101891151, under the same conditions (with the MgCl of 0.5mol/L at 25 DEG C
2solution reaction 90min), hydrogen output and produce hydrogen rate and improve more than 1 times that (hydrogen desorption capacity of magnesium-aluminum-based hydride composite is 680ml/g, produce hydrogen rate and be only 45.0%, and magnesium calcium base hydride hydrogen desorption capacity of the present invention is 1450ml/g, producing hydrogen rate is 94.1%, sees embodiment 16).Thus magnesium calcium base hydride powder of the present invention has well taken into account the security of reacting, controllability and actual hydrogen output, in particular improve the hydrogen output under room temperature and low temperature and produce hydrogen rate, there is good ambient adaptability and practicality, be a kind of wide warm area hydrolytic hydrogen production magnesium calcium base hydride powder well, moistening high-purity hydrogen source can better be provided for fuel cell or hydrogen internal combustion engine.
2, the present invention adopts cheap magnesium calcium alloy to be raw material, by ball milling powder process after the fragmentation of magnesium calcium alloy, reduce the granularity of alloy powder particle, improve specific surface area and the surfactivity of alloying pellet, increase the defect of alloying pellet inside, thus reduce the hydrogenation conditions of alloy, be conducive to industrialized production.Alloy has rough surface and loose porous grain pattern by the magnesium calcium base hydride powder that after ball milling, hydrogenation obtains again simultaneously, large specific surface area and more hole, for the hydrolysis reaction of magnesium calcium base hydride powder provides more reaction interface and passage, be conducive to hydrolysis reaction and be tending towards complete, the actual hydrogen desorption capacity of further raising and product hydrogen rate, particularly also have good hydrogen output and produce hydrogen rate under room temperature and low temperature.
3, magnesium calcium base hydride powder of the present invention is through independent mechanical ball milling process, or after adding second-phase (other hydride are with ∕ salt) carrying out mechanical ball milling, reduce particle size, increase the specific surface area of powder, and form a large amount of defects, for hydrolysis provides larger reaction interface and more reaction channel, further increase actual hydrogen desorption capacity and produce hydrogen rate, particularly also there is higher hydrogen output under room temperature and low temperature and produce hydrogen rate.
4, the hydrolysising by-product of magnesium calcium base hydride powder of the present invention is environmentally friendly, and the by product after hydrolysis reaction is mainly with Mg (OH)
2, Ca (OH)
2exist etc. form, environmentally safe, wherein Mg (OH)
2with Ca (OH)
2also can be used as flame-retardant additive to use.
5, the present invention adopts cheap magnesium calcium alloy as raw material, and magnesium calcium alloy contains easy crisp phase Mg
2ca, solves the problem of magnesium, calcium elemental metals powder process difficulty, and with low cost, is easy to realize industrialization.
Accompanying drawing explanation
Fig. 1 is SEM figure (scanning electron microscope (SEM) photograph) of the magnesium calcium base hydride powder that embodiment 1 obtains;
Fig. 2 is the XRD figure of the magnesium calcium base hydride powder that embodiment 4 obtains;
Fig. 3 is the hydrolysis Hydrogen desorption isotherms of magnesium calcium base hydride powder 50 DEG C time that embodiment 7 obtains;
Fig. 4 is the sedimentary XRD figure of gained after embodiment 7 hydrolysis reaction.
Embodiment
Below by embodiment, magnesium calcium base hydride powder of the present invention and preparation method thereof is described further.
Embodiment 1
By calcic 35wt%, magnesium calcium alloy containing magnesium 65wt% is crushed to and is less than 200 orders, and in argon gas atmosphere, ratio of grinding media to material is ball milling 2h under 20:1 condition, then ball milling gained powder is placed in Sieverts-type(Xi Fucishi) device, it is 400 DEG C in temperature, hydrogen pressure is activate 4 times under 4MPa condition, then inhales hydrogen hydrogenation 24h, obtains magnesium calcium base hydride powder, its SEM figure is shown in Fig. 1, wherein magnesium calcium hydride Ca
4mg
3h
14for 50.2wt%, magnesium hydride MgH
2for 47.3wt%, surplus Mg is 2.5wt%.
Get the reactor that magnesium calcium base hydride powder that 0.2g obtains is placed in constant temperature 0 DEG C, injecting 10ml temperature is that the distilled water of 0 DEG C reacts, and adopts draining water gathering of gas law to collect hydrogen, reaction 60min.Convert often gram of above-mentioned materials produces hydrogen 775ml.
Embodiment 2
By calcic 25wt%, magnesium calcium alloy containing magnesium 75wt% is crushed to and is less than 300 orders, and in argon gas atmosphere, ratio of grinding media to material is ball milling 3h under 20:1 condition, then ball milling gained powder is placed in Sieverts-type(Xi Fucishi) device, temperature 400 DEG C, hydrogen pressure is activate 4 times under 4.5MPa condition, inhale hydrogen hydrogenation 6h again, obtain magnesium calcium base hydride powder, wherein magnesium calcium hydride Ca
4mg
3h
14for 35.8wt%, magnesium hydride MgH
2for 61.5wt%, surplus Mg is 2.7wt%.
Get the reactor that magnesium calcium base hydride powder that 0.2g obtains is placed in constant temperature 10 DEG C, injecting 10ml temperature is that the distilled water of 10 DEG C reacts, and adopts draining water gathering of gas law to collect hydrogen, reaction 60min.Convert often gram of above-mentioned materials produces hydrogen 585ml.
Embodiment 3
(1) by calcic 35wt%, magnesium calcium alloy containing magnesium 65wt% is crushed to and is less than 100 orders, and in argon gas atmosphere, ratio of grinding media to material is ball milling 1h under 8:1 condition, then the powder of ball milling gained is placed in Sieverts-type(Xi Fucishi) device is 400 DEG C in temperature, hydrogen pressure is activate 1 time under 3.5MPa condition, inhale hydrogen hydrogenation 24h again, obtain magnesium calcium base hydride powder, wherein magnesium calcium hydride Ca
4mg
3h
1450.2wt%, magnesium hydride MgH
2for 34.8wt%, surplus Mg is 15.0wt%.
(2) by gained magnesium calcium base hydride powder in ball mill, under argon gas atmosphere, with ratio of grinding media to material 2:1 mechanical ball milling 10h.
Get the reactor that magnesium calcium base hydride powder that 0.2g obtains is placed in constant temperature 25 DEG C, injecting 10ml temperature is that the distilled water of 25 DEG C reacts, and adopts draining water gathering of gas law to collect hydrogen, reaction 60min.After converting, every gram of above-mentioned materials puts hydrogen 1350ml.
Embodiment 4
(1) by calcic 20wt%, magnesium calcium alloy containing magnesium 80wt% is crushed to and is less than 50 orders, and under argon gas atmosphere, ratio of grinding media to material are 30:1 condition ball milling 0.5h, then ball milling gained powder is placed in Sieverts-type(Xi Fucishi) device, it is 400 DEG C in temperature, hydrogen pressure is do not carry out under 5MPa condition activating directly inhaling hydrogen hydrogenation 24h, obtains magnesium calcium base hydride powder (XRD analysis is shown in Fig. 2), wherein magnesium calcium hydride Ca
4mg
3h
14for 28.6wt%, magnesium hydride MgH
2for 56.7wt%, surplus is Mg is 14.7wt%.
(2) by gained magnesium calcium base hydride powder in ball mill, under argon gas atmosphere, with ratio of grinding media to material 60:1 mechanical ball milling 10min.
Get the reactor that magnesium calcium base hydride powder that 0.2g obtains is placed in constant temperature 50 DEG C, injecting 10ml temperature is that the distilled water of 50 DEG C reacts, and adopts draining water gathering of gas law to collect hydrogen, reaction 60min.After converting, every gram of above-mentioned materials puts hydrogen 1220ml.
Embodiment 5
By calcic 20wt%, magnesium calcium alloy containing magnesium 80wt% is crushed to and is less than 50 orders, and under argon gas atmosphere, ratio of grinding media to material are 30:1 condition ball milling 0.5h, then ball milling gained powder is placed in Sieverts-type(Xi Fucishi) device, it is 400 DEG C in temperature, hydrogen pressure is do not carry out under 5MPa condition activating directly inhaling hydrogen hydrogenation 24h, obtains magnesium calcium base hydride powder, wherein magnesium calcium hydride Ca
4mg
3h
14for 28.6wt%, magnesium hydride MgH
2for 56.7wt%, surplus is Mg is 14.7wt%.
Get the reactor that magnesium calcium base hydride powder that 0.2g obtains is placed in constant temperature 70 DEG C, injecting 10ml temperature is that the distilled water of 70 DEG C reacts, and adopts draining water gathering of gas law to collect hydrogen, reaction 60min.After converting, every gram of above-mentioned materials puts hydrogen 1515ml.
Embodiment 6
By calcic 15wt%, magnesium calcium alloy containing magnesium 85wt% is crushed to and is less than 300 orders, and under argon gas atmosphere, ratio of grinding media to material are 60:1 condition ball milling 2h, then ball milling gained powder is placed in Sieverts-type(Xi Fucishi) device, be 350 DEG C in temperature, hydrogen pressure is activate 3 times under 3.5MPa condition, then inhales hydrogen hydrogenation 12h, obtain magnesium calcium base hydride powder, wherein magnesium calcium hydride Ca
4mg
3h
14for 21.4wt%, magnesium hydride MgH
2for 73.3wt%, surplus Mg is 5.3wt%.
Get the reactor that magnesium calcium base hydride powder that 0.2g obtains is placed in constant temperature 85 DEG C, injecting 10ml temperature is that the distilled water of 85 DEG C reacts, and adopts draining water gathering of gas law to collect hydrogen, reaction 60min.After converting, every gram of above-mentioned materials puts hydrogen 1565ml.
Embodiment 7
(1) by calcic 20wt%, magnesium calcium alloy containing magnesium 80wt% is crushed to and is less than 50 orders, and in argon gas atmosphere, ratio of grinding media to material is ball milling 0.5h under the condition of 30:1, then ball milling gained powder is placed in Sieverts-type(Xi Fucishi) device, be 400 DEG C in temperature, hydrogen pressure is do not carry out under 5MPa condition activating directly inhaling hydrogen hydrogenation 24h, both magnesium calcium base hydride powder, wherein magnesium calcium hydride Ca was obtained
4mg
3h
14for 28.6wt%, magnesium hydride MgH
2for 56.7wt%, surplus Mg is 14.7wt%.
(2) by gained magnesium calcium base hydride powder in ball mill, under argon gas atmosphere, with ratio of grinding media to material 20:1 mechanical ball milling 1h.
Get the reactor that magnesium calcium base hydride powder that 0.2g obtains is placed in constant temperature 50 DEG C, injecting 10ml temperature is that the distilled water of 50 DEG C reacts, and adopt draining water gathering of gas law to collect hydrogen, reaction 60min, hydrolysis Hydrogen desorption isotherms is shown in Fig. 3.After converting, every gram of above-mentioned materials puts hydrogen 1375ml.
Question response filters to obtain canescence material completely afterwards, and after secondary with distilled water flushing filter 23, at 60 DEG C, vacuum-drying obtains pale powder, utilizes XRD analysis (the results are shown in Figure 4) pale powder to be magnesium hydroxide and calcium hydroxide.
Embodiment 8
(1) by calcic 10wt%, magnesium calcium alloy containing magnesium 90wt% is crushed to and is less than 50 orders, and in argon gas atmosphere, ratio of grinding media to material is ball milling 3h under 60:1 condition, then ball milling gained powder is placed in Sieverts-type(Xi Fucishi) device, temperature 450 DEG C, activate 2 times under hydrogen pressure 3MPa condition, inhale hydrogen hydrogenation 24h again, obtain magnesium calcium base hydride powder, wherein magnesium calcium hydride Ca
4mg
3h
14for 14.2wt%, magnesium hydride MgH
2for 78.1wt%, surplus Mg is 7.7wt%.
(2) with the magnesium calcium base hydride powder obtained by step (1) and MgSO
4for raw material, MgSO
4the magnesium calcium base hydride powder quality of content prepared by step (1) 11%, in the glove box of argon gas atmosphere, take MgSO
4, it is placed in ball grinder together with the magnesium calcium base hydride powder obtained by step (1), adopts ball mill under an argon atmosphere with ratio of grinding media to material 60:1 mechanical ball milling 10min, obtain being compounded with MgSO
4magnesium calcium base hydride powder.
Get 0.2g and be compounded with MgSO
4magnesium calcium base hydride powder be placed in the reactor of constant temperature 40 DEG C, injecting 10ml temperature is that the distilled water of 40 DEG C reacts, and adopts draining water gathering of gas law to collect hydrogen, reaction 60min.After converting, every gram of above-mentioned materials puts hydrogen 525ml.
Embodiment 9
(1) by calcic 15wt%, magnesium calcium alloy containing magnesium 85wt% is crushed to and is less than 300 orders, and in argon gas atmosphere, ratio of grinding media to material is ball milling 2h under 60:1 condition, then ball milling gained powder is placed in Sieverts-type(Xi Fucishi) device, temperature 350 DEG C, activate 3 times under hydrogen pressure 3.5MPa condition, inhale hydrogen hydrogenation 12h again, obtain magnesium calcium base hydride powder, wherein magnesium calcium hydride Ca
4mg
3h
14for 21.4wt%, magnesium hydride MgH
2for 73.3wt%, surplus Mg is 5.3wt%.
(2) with the magnesium calcium base hydride powder obtained by step (1) and NaAlH
4for raw material, NaAlH
4the magnesium calcium base hydride powder quality of content prepared by step (1) 5%, in the glove box of argon gas atmosphere, take NaAlH
4, it is placed in ball grinder together with the magnesium calcium base hydride powder obtained by step (1), adopts ball mill under an argon atmosphere with ratio of grinding media to material 2:1 mechanical ball milling 0.5h, obtain being compounded with NaAlH
4magnesium calcium base hydride powder.
Get 0.2g and be compounded with NaAlH
4magnesium calcium base hydride powder be placed in the reactor of constant temperature 0 DEG C, injecting 10ml temperature is that the distilled water of 0 DEG C reacts, and adopts draining water gathering of gas law to collect hydrogen, reaction 60min.After converting, every gram of above-mentioned materials puts hydrogen 550ml.
Embodiment 10
(1) by calcic 15wt%, magnesium calcium alloy containing magnesium 85wt% is crushed to and is less than 300 orders, and in argon gas atmosphere, ratio of grinding media to material is ball milling 2h under 60:1 condition, then ball milling gained powder is placed in Sieverts-type(Xi Fucishi) device, temperature 350 DEG C, activate 3 times under hydrogen pressure 3.5MPa condition, inhale hydrogen hydrogenation 12h again, obtain magnesium calcium base hydride powder, wherein magnesium calcium hydride Ca
4mg
3h
14for 21.4wt%, magnesium hydride MgH
2for 73.3wt%, surplus Mg is 5.3wt%.
(2) with the magnesium calcium base hydride powder obtained by step (1) and NaH for raw material, 3% of the magnesium calcium base hydride powder quality of content prepared by step (1) of NaH, NaH is taken in the glove box of argon gas atmosphere, it is placed in ball grinder together with the magnesium calcium base hydride powder obtained by step (1), adopt ball mill under an argon atmosphere with ratio of grinding media to material 10:1 mechanical ball milling 0.5h, obtain the magnesium calcium base hydride powder being compounded with NaH.
Get the reactor that magnesium calcium base hydride powder that 0.2g is compounded with NaH is placed in constant temperature 0 DEG C, injecting 10ml temperature is that the distilled water of 0 DEG C reacts, and adopts draining water gathering of gas law to collect hydrogen, reaction 60min.After converting, every gram of above-mentioned materials puts hydrogen 478ml.
Embodiment 11
(1) by calcic 10wt%, magnesium calcium alloy containing magnesium 90wt% is crushed to and is less than 50 orders, and in argon gas atmosphere, ratio of grinding media to material is ball milling 3h under 60:1 condition, then ball milling gained powder is placed in Sieverts-type(Xi Fucishi) device is 450 DEG C in temperature, hydrogen pressure is activate 2 times under 3MPa condition, inhale hydrogen hydrogenation 24h again, obtain magnesium calcium base hydride powder, wherein magnesium calcium hydride Ca
4mg
3h
14for 14.2wt%, magnesium hydride MgH
2for 78.1wt%, surplus Mg is 7.7wt%.
(2) with the magnesium calcium base hydride powder obtained by step (1), NaCl and KCl is raw material, 5.7% of the magnesium calcium base hydride powder quality of content prepared by step (1) of NaCl, 3.0% of the magnesium calcium base hydride powder quality of content prepared by step (1) of KCl, NaCl and KCl is taken in the glove box of argon gas atmosphere, it is placed in ball grinder together with the magnesium calcium base hydride powder obtained by step (1), adopt ball mill under an argon atmosphere with ratio of grinding media to material 30:1 mechanical ball milling 10h, obtain the magnesium calcium base hydride powder being compounded with NaCl and KCl.
Get the reactor that magnesium calcium base hydride powder that 0.2g is compounded with NaCl and KCl is placed in constant temperature 25 DEG C, injecting 10ml temperature is that the distilled water of 25 DEG C reacts, and adopts draining water gathering of gas law to collect hydrogen, reaction 60min.After converting, every gram of above-mentioned materials puts hydrogen 400ml.
Embodiment 12
(1) by calcic 10wt%, magnesium calcium alloy containing magnesium 90wt% is crushed to and is less than 50 orders, and in argon gas atmosphere, ratio of grinding media to material is ball milling 3h under 60:1 condition, then ball milling gained powder is placed in Sieverts-type(Xi Fucishi) device, temperature 450 DEG C, activate 2 times under hydrogen pressure 3MPa condition, inhale hydrogen hydrogenation 24h again, obtain magnesium calcium base hydride powder, wherein magnesium calcium hydride Ca
4mg
3h
14for 14.2wt%, magnesium hydride MgH
2for 78.1wt%, surplus Mg is 7.7wt%.
(2) with magnesium calcium base hydride powder, the AlCl obtained by step (1)
3and LiAlH
4for raw material, AlCl
3the magnesium calcium base hydride powder quality of content prepared by step (1) 11%, LiAlH
4the magnesium calcium base hydride powder quality of content prepared by step (1) 2%, in the glove box of argon gas atmosphere, take AlCl
3and LiAlH
4, it is placed in ball grinder together with the magnesium calcium base hydride powder obtained by step (1), adopts ball mill under an argon atmosphere with ratio of grinding media to material 60:1 mechanical ball milling 0.5h, obtain being compounded with AlCl
3and LiAlH
4magnesium calcium base hydride powder.
Get 0.2g and be compounded with AlCl
3and LiAlH
4magnesium calcium base hydride powder be placed in the reactor of constant temperature 30 DEG C, injecting 10ml temperature is that the distilled water of 30 DEG C reacts, and adopts draining water gathering of gas law to collect hydrogen, reaction 60min.After converting, every gram of above-mentioned materials puts hydrogen 575ml.
Embodiment 13
(1) by calcic 15wt%, magnesium calcium alloy containing magnesium 85wt% is crushed to and is less than 300 orders, and in argon gas atmosphere, ratio of grinding media to material is ball milling 2h under 60:1 condition, then ball milling gained powder is placed in Sieverts-type(Xi Fucishi) device, temperature 350 DEG C, activate 3 times under hydrogen pressure 3.5MPa condition, inhale hydrogen hydrogenation 12h again, obtain magnesium calcium base hydride powder, wherein magnesium calcium hydride Ca
4mg
3h
14for 21.4wt%, magnesium hydride MgH
2for 73.3wt%, surplus Mg is 5.3wt%.
(2) with magnesium calcium base hydride powder, the NaAlH obtained by step (1)
4be raw material with KH, NaAlH
4the magnesium calcium base hydride powder quality of content prepared by step (1) 2.5%, KH the magnesium calcium base hydride powder quality of content prepared by step (1) 2.5%, in the glove box of argon gas atmosphere, take NaAlH
4and KH, it is placed in ball grinder together with the magnesium calcium base hydride powder obtained by step (1), adopts ball mill under an argon atmosphere with ratio of grinding media to material 10:1 mechanical ball milling 10min, obtain being compounded with NaAlH
4with KH magnesium calcium base hydride powder.
Get 0.2g and be compounded with NaAlH
4be placed in the reactor of constant temperature 0 DEG C with the magnesium calcium base hydride powder of KH, injection 10ml temperature is that the distilled water of 0 DEG C reacts, and adopts draining water gathering of gas law to collect hydrogen, reaction 60min.After converting, every gram of above-mentioned materials puts hydrogen 565ml.
Embodiment 14
(1) by calcic 10wt%, magnesium calcium alloy containing magnesium 90wt% is crushed to and is less than 150 orders, and in argon gas atmosphere, ratio of grinding media to material is ball milling 5h under 40:1 condition, then ball milling gained powder is placed in Sieverts-type(Xi Fucishi) device, temperature 500 DEG C, hydrogen pressure is activate 5 times under 6MPa condition, inhale hydrogen hydrogenation 24h again, obtain magnesium calcium base hydride powder, wherein magnesium calcium hydride Ca
4mg
3h
14for 14.2wt%, magnesium hydride MgH
2for 85.7wt%, surplus Mg is 0.1wt%.
(2) with the magnesium calcium base hydride powder obtained by step (1), NaH, MgF
2and MgCl
2for raw material, 3%, MgF of the magnesium calcium base hydride powder quality of content prepared by step (1) of NaH
2the magnesium calcium base hydride powder quality of content prepared by step (1) 3%, MgCl
2the magnesium calcium base hydride powder quality of content prepared by step (1) 5%, in the glove box of argon gas atmosphere, take NaH, MgF
2and MgCl
2, it is placed in ball grinder together with the magnesium calcium base hydride powder obtained by step (1), adopts ball mill under an argon atmosphere with ratio of grinding media to material 10:1 mechanical ball milling 3h, obtain being compounded with NaH, MgF
2and MgCl
2magnesium calcium base hydride powder.
Get 0.2g and be compounded with NaH, MgF
2and MgCl
2magnesium calcium base hydride powder be placed in the reactor of constant temperature 30 DEG C, injecting 10ml temperature is that the distilled water of 30 DEG C reacts, and adopts draining water gathering of gas law to collect hydrogen, reaction 60min.After converting, every gram of above-mentioned materials puts hydrogen 585ml.
Embodiment 15
(1) by calcic 25wt%, magnesium calcium alloy containing magnesium 75wt% is crushed to and is less than 300 orders, and in argon gas atmosphere, ratio of grinding media to material is ball milling 3h under 20:1 condition, then ball milling gained powder is placed in Sieverts-type(Xi Fucishi) device, temperature 400 DEG C, hydrogen pressure is activate 4 times under 4.5MPa condition, inhale hydrogen hydrogenation 6h again, obtain magnesium calcium base hydride powder, wherein magnesium calcium hydride Ca
4mg
3h
14for 35.8wt%, magnesium hydride MgH
2for 61.5wt%, surplus Mg is 2.7wt%.
(2) with magnesium calcium base hydride powder, the CaCl obtained by step (1)
2with Mg (NO
3)
2for raw material, CaCl
23%, Mg (NO of the magnesium calcium base hydride powder quality of content prepared by step (1)
3)
2the magnesium calcium base hydride powder quality of content prepared by step (1) 5%, in the glove box of argon gas atmosphere, take CaCl
2with Mg (NO
3)
2, it is placed in ball grinder together with the magnesium calcium base hydride powder obtained by step (1), adopts ball mill under an argon atmosphere with ratio of grinding media to material 20:1 mechanical ball milling 3h, obtain being compounded with CaCl
2with Mg (NO
3)
2magnesium calcium base hydride powder.
Get 0.2g and be compounded with CaCl
2with Mg (NO
3)
2magnesium calcium base hydride powder be placed in the reactor of constant temperature 0 DEG C, injecting 10ml temperature is that the distilled water of 0 DEG C reacts, and adopts draining water gathering of gas law to collect hydrogen, reaction 60min.After converting, every gram of above-mentioned materials puts hydrogen 525ml.
Embodiment 16
By calcic 25wt%, magnesium calcium alloy containing magnesium 75wt% is crushed to and is less than 300 orders, and in argon gas atmosphere, ratio of grinding media to material is ball milling 3h under 20:1 condition, then ball milling gained powder is placed in Sieverts-type(Xi Fucishi) device, temperature 400 DEG C, hydrogen pressure is activate 4 times under 4.5MPa condition, inhale hydrogen hydrogenation 6h again, obtain magnesium calcium base hydride powder, wherein magnesium calcium hydride Ca
4mg
3h
14for 35.8wt%, magnesium hydride MgH
2for 61.5wt%, surplus Mg is 2.7wt%.
Get the reactor that 0.2g magnesium calcium base hydride powder is placed in constant temperature 25 DEG C, inject the MgCl that 10ml temperature is the 0.5mol/L of 25 DEG C
2the aqueous solution reacts, and adopts draining water gathering of gas law to collect hydrogen, reaction 60min.After converting, every gram of above-mentioned materials puts hydrogen 1450ml.
Embodiment 17
By calcic 25wt%, magnesium calcium alloy containing magnesium 75wt% is crushed to and is less than 300 orders, and in argon gas atmosphere, ratio of grinding media to material is ball milling 3h under 20:1 condition, then ball milling gained powder is placed in Sieverts-type(Xi Fucishi) device, temperature 400 DEG C, hydrogen pressure is activate 4 times under 4.5MPa condition, inhale hydrogen hydrogenation 6h again, obtain magnesium calcium base hydride powder, wherein magnesium calcium hydride Ca
4mg
3h
14for 35.8wt%, magnesium hydride MgH
2for 61.5wt%, surplus Mg is 2.7wt%.
Get the reactor that 0.2g magnesium calcium base hydride powder is placed in constant temperature 0 DEG C, injection 10ml temperature is that the aqueous citric acid solution of the 0.5mol/L of 0 DEG C reacts, and adopts draining water gathering of gas law to collect hydrogen, reaction 60min.After converting, every gram of above-mentioned materials puts hydrogen 1541ml.
Embodiment 18
By calcic 35wt%, magnesium calcium alloy containing magnesium 65wt% is crushed to and is less than 200 orders, and in argon gas atmosphere, ratio of grinding media to material is ball milling 4h under 20:1 condition, then ball milling gained powder is placed in Sieverts-type(Xi Fucishi) device, temperature 450 DEG C, activate 4 times under hydrogen pressure 5MPa condition, inhale hydrogen hydrogenation 24h again, obtain magnesium calcium base hydride powder, wherein magnesium calcium hydride Ca
4mg
3h
14for 50.2wt%, magnesium hydride MgH
2for 49.3wt%, surplus Mg is 0.5wt%.
Getting 0.2g magnesium calcium base hydride powder, to be placed in constant temperature be in the low-temp reaction device of-10 DEG C, and injecting 10ml temperature is that 50% aqueous ethanolic solution (V/V) of-10 DEG C reacts, and adopts draining water gathering of gas law to collect hydrogen, reaction 60min.After converting, every gram of above-mentioned materials puts hydrogen 675ml.
Claims (10)
1., for a magnesium calcium base hydride powder for hydrolytic hydrogen production, the mass percent of the component comprised and each component is:
Ca
4Mg
3H
1414.2～50.2%，
MgH
234.8～85.7%，
Mg0.1～15%。
2. magnesium calcium base hydride powder according to claim 1, it is characterized in that also being compounded with other hydride with ∕ or salt, the content of other hydride described is Ca
4mg
3h
14, MgH
2with 0 ~ 5% of Mg total mass, the content of salt is Ca
4mg
3h
14, MgH
2with 0 ~ 11% of Mg total mass, wherein, be 0 when the content of the content of other hydride, salt is different.
3. magnesium calcium base hydride powder according to claim 2, is characterized in that other hydride described is that alkalimetal hydride is with ∕ or alanate.
4. magnesium calcium base hydride powder according to claim 3, is characterized in that described alkalimetal hydride is that sodium hydride is with ∕ or potassium hydride KH; Described alanate is that sodium alanate is with ∕ or aluminium lithium hydride.
5. magnesium calcium base hydride powder according to claim 2, is characterized in that described salt is at least one in sodium-chlor, aluminum chloride, Repone K, calcium chloride, magnesium chloride, magnesium fluoride, magnesium sulfate, magnesium nitrate.
6. magnesium calcium base hydride raw powder's production technology described in claim 1, is characterized in that processing step is as follows:
Be 10 ~ 35% by calcium mass percent, magnesium mass percent be 65 ~ 90% magnesium calcium alloy be crushed to and be less than 50 ~ 300 orders, then be (8 ~ 60) in argon gas atmosphere, ratio of grinding media to material: ball milling 0.5 ~ 5h under the condition of 1, continue after by ball milling gained magnesium calcium alloy powder 350 ~ 500 DEG C, activation 0 ~ 5 time under hydrogen pressure 3 ~ 6MPa, inhale hydrogen hydrogenation 6 ~ 24h again, obtaining component is Ca
4mg
3h
14, MgH
2with the magnesium calcium base hydride powder of Mg.
7. magnesium calcium base hydride raw powder's production technology according to claim 6, is characterized in that the component to obtaining after inhaling hydrogen hydrogenation is Ca
4mg
3h
14, MgH
2be (2 ~ 60) with the magnesium calcium base hydride powder of Mg in argon gas atmosphere, ratio of grinding media to material: ball milling 10min ~ 10h under the condition of 1.
8. magnesium calcium base hydride raw powder's production technology described in arbitrary claim in claim 2 to 5, it is characterized in that with the magnesium calcium base hydride powder prepared by claim 6, other hydride is with ∕ or salt are raw material, 0 ~ 5% of the magnesium calcium base hydride powder quality of content prepared by claim 6 of other hydride described, 0 ~ 11% of the magnesium calcium base hydride powder quality of content prepared by claim 6 of salt, wherein, the content of other hydride, the content of salt is 0 time different, processing step is as follows: by the magnesium calcium base hydride powder prepared by the claim 6 that measures, other hydride is with ∕ or salt add in ball mill, in argon gas atmosphere, ratio of grinding media to material is (2 ~ 60): ball milling 10min ~ 10h under the condition of 1.
9. magnesium calcium base hydride raw powder's production technology according to claim 8, is characterized in that other hydride described are that alkalimetal hydride is with ∕ or alanate; Described salt is at least one in sodium-chlor, aluminum chloride, Repone K, calcium chloride, magnesium chloride, magnesium fluoride, magnesium sulfate, magnesium nitrate.
10. magnesium calcium base hydride raw powder's production technology according to claim 9, is characterized in that described alkalimetal hydride is that sodium hydride is with ∕ or potassium hydride KH; Described alanate is that sodium alanate is with ∕ or aluminium lithium hydride.
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| CN102390805A (en) * | 2011-08-24 | 2012-03-28 | 中山大学 | Hydrogen production composition and preparation method thereof, and method for preparing hydrogen |
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| CN102390805A (en) * | 2011-08-24 | 2012-03-28 | 中山大学 | Hydrogen production composition and preparation method thereof, and method for preparing hydrogen |
Non-Patent Citations (2)
| Title |
|---|
| Magnesium based ternary metal hydrides containing alkali and alkaline-earth elements;Klaus Yvon et al.;《Journal of Alloys and Compounds》;20060228;第425卷;第102页左栏第1段 * |
| Tetracalcium trimagnesium tetradecahydride,Ca4Mg3H14:the first ternary alkaline earth hydride;F. Gingl et al.;《Journal of Alloys and Compounds》;19921231;第185卷;第273-278页 * |
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