CN101830431A - Method for preparing hydrogen by taking boron hydride ammino complex as hydrogen source - Google Patents

Method for preparing hydrogen by taking boron hydride ammino complex as hydrogen source Download PDF

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Publication number
CN101830431A
CN101830431A CN200910047260A CN200910047260A CN101830431A CN 101830431 A CN101830431 A CN 101830431A CN 200910047260 A CN200910047260 A CN 200910047260A CN 200910047260 A CN200910047260 A CN 200910047260A CN 101830431 A CN101830431 A CN 101830431A
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hydrogen
promotor
hydroborates
ammonia complex
ammonia
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CN200910047260A
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余学斌
郭艳辉
夏广林
高梁
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Fudan University
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Fudan University
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Abstract

The invention belongs to the technical field of new material and energy development, in particular to a method for preparing hydrogen by taking a boron hydride ammino complex as a hydrogen source. In the invention, the hydrogen is prepared by taking the boron hydride ammino complex [M(BH4)n.xNH3] as the hydrogen source. The method comprises the following steps of: mixing the [M(BH4)n.xNH3] with a hydrogen release promoter thereof, then carrying out ball milling or heating to a certain temperature, stirring and mixing to prepare a compound hydrogen release system, and heating the hydrogen release system to a certain temperature to prepare the hydrogen. The invention has simple process and convenient synthesis; the obtained composite has certain adaptability to the environment and can be heated in air to release the hydrogen; and the initial hydrogen release temperature, the hydrogen release speed and the hydrogen capability of the obtained composite can be regulated and controlled within a certain range.

Description

A kind of is the method that hydrogen source is produced hydrogen with the hydroborates ammonia complex
Technical field
The invention belongs to novel material and field of energy source developing technology, be specifically related to a kind of preparation method of hydrogen, is the method that hydrogen source is produced hydrogen with the hydroborates ammonia complex particularly.
Background technology
Energy problem is the big problem that the China and the world today face jointly.Along with going deep into of development and national economy and urbanization construction, energy problem is obvious day by day to the restriction of Economic development and people's living standard raising aspect.The main body of the energy is the fossil oil of Nonrenewable resources at present, but exists it not enough in many ways as energy source: at first, this form generation economic benefit of utilizing is very low; Secondly, fossil oil is followed the pollution of various ways in the production capacity process; Moreover along with the continuous exhaustion of its reserves, it is that the application of others has brought many pressure as form of energy consumption.Hydrogen Energy possesses the energy density height, and cleanliness without any pollution is renewable, is convenient to advantages such as form of energy conversion, is the optimal carrier of the energy, becomes a research focus of energy development aspect.
The emphasis of storage hydrogen research is the novel high-capacity hydrogen storage material that exploitation can be satisfied the fuel cells applications needs in the Hydrogen Energy system, and its technical indicator is that storage hydrogen weight ratio is more than 6%.Along with the hydrogen expanding economy, many hydrogen storage materials constantly are developed, as alloy, and light metal hydride, carbon nanotube etc.But the limitation that does not break through is as yet separately all arranged in the material of having developed, hindered their application: not high as alloy storage hydrogen weight ratio, light metal hydride, hydrogen discharges and the regeneration condition harshness, and the nano material energy storage is limited etc.
In many ways discover to have superior hydrogen discharging performance with the material that contains nominal price hydrogen and negative valency hydrogen in a part.Representational material is ammonia borane (NH in this class material 3BH 3) and series material such as LiNH 2BH 3And light metal hydride ammonia complex such as Mg (BH 4) 22NH 3NH 3BH 3(hydrogen richness 19.6wt%) can slowly put hydrogen, LiNH below 100 ℃ 2BH 3(hydrogen richness 13.6wt%) can be at 100 ℃ of hydrogen of emitting 7wt% with fast speeds, Mg (BH 4) 22NH 3(hydrogen richness 16.0wt%) just begins to decompose release hydrogen in the time of 150 ℃.
Summary of the invention
The object of the present invention is to provide a kind of is the method that hydrogen source is produced hydrogen with the hydroborates ammonia complex, and then provide a class novel put hydrogen system, this system has certain adaptability to external environment, and can begin release hydrogen below 100 ℃, the convenient use.
Purpose of the present invention realizes by following method and step:
The present invention is with hydroborates ammonia complex (M (BH 4) nXNH 3) produce hydrogen for hydrogen source, with M (BH 4) nXNH 3With put hydrogen promotor mix the back ball milling or be heated to certain temperature mix the preparation the compound hydrogen system of putting, this system is heated to certain temperature gets final product release hydrogen.
Hydroborates M (BH in the hydroborates ammonia complex of the present invention 4) n,, mainly comprise LiBH for carrying out the compound of complexing with ammonia 4, Ca (BH 4) 2, Mg (BH 4) 2, Zn (BH 4) 2, Be (BH 4) 2, Ni (BH 4) 2Deng; Its ammonia complex M (BH 4) nXNH 3For all stable ammonia complexs of described hydroborates, as LiBH 4XNH 3(3 〉=x＞0), Mg (BH 4) 2XNH 3(6 〉=x＞0) etc.
Of the present invention put hydrogen promotor be mainly can with the material of ammonia generation complexing action, the mixture of one or more of the ammonia complex of such material and mesoporous material.The material of putting in the hydrogen promotor with ammonia generation complexing mainly comprises Zn 2+, Ca 2+, Mg 2+, Cu 2+, Ni 2+, Li 2+Deng muriate, hydrosulfate, fluorochemical, hydride, hydroborate etc.; Mesoporous material comprises SiO 2, CNT (carbon nano-tube), BN nanotube, molecular sieve, mould material etc.Mesoporous material can use separately or use jointly with the Ammonia complex compound
In the present invention, when promotor is used ammonia complex matter, itself and M (BH 4) nXNH 3Compound, can be with ball milled or heating method; When promotor is used mesoporous material, itself and LiBH 4XNH 3Compound need heating method.With promotor and M (BH 4) nXNH 3Mix, and the process of preparation mixture is preferably under the atmosphere of anhydrous and oxygen-free and carries out, as nitrogen, inert atmospheres such as argon gas.With ball milled with promotor and M (BH 4) nXNH 3During mixing, the ball milling time should be no less than 5 minutes, and the proper extension ball milling time can guarantee uniform mixing, and the ball milling temperature should not be higher than the decomposition temperature of used material.During with the heating method mixing raw material, Heating temperature should be between used M (BH 4) nXNH 3Fusing point and decomposition temperature between, decomposition temperature is lower than the material of fusing point can not use heating method.As use LiBH 4NH 3Compound tense, use temperature should be higher than 60 ℃, LiBH 42NH 3Should be higher than 16 ℃, LiBH 43NH 3Should be higher than 30 ℃.Should stir in the heat-processed, or carry out ultra-sonic dispersion.
At preparation hydroborates ammonia complex when putting that hydrogen promotor is compound puts hydrogen system, promotor and M (BH 4) nXNH 3Weight ratio should be not less than 1: 10, and the consumption that suitably improves promotor can reduce or suppress M (BH fully 4) nXNH 3Decompose the reaction that discharges ammonia.
Hydroborates ammonia complex of the present invention and put the compound hydrogen system of putting of hydrogen promotor and can heat in rare gas element and vacuum makes its release hydrogen, and the part mixture has certain stability in air, also can heat hydrogen is emitted in air.
In the present invention, the initial hydrogen discharging temperature of preparation gained mixture is usually less than 100 ℃, the temperature of concrete initial release hydrogen, speed and hydrogen desorption capacity can suitably be controlled by kind and the consumption of regulating promotor, wherein use hydroborate and ammonia complex thereof can obtain the system of high hydrogen content as promotor.
The present invention has the following aspects remarkable advantage:
1), technology is simple, synthetic convenient.
2), technology is not high to equipment requirements, be easy to realize.
3), the gained mixture has certain adaptability to environment, can heat release hydrogen in air.
4), initial hydrogen discharging temperature, hydrogen discharging rate and the hydrogen capacity of gained mixture can be regulated and control within the specific limits.
Description of drawings
Fig. 1 is LiBH 4NH 3The TG-MS spectrogram.
Fig. 2 is LiBH 4NH 3With MgCl 2The TG-MS spectrogram of compound system.
Fig. 3 is LiBH 4NH 3With ZnCl 2The TG-MS spectrogram of compound system.
Fig. 4 is LiBH 4NH 3With CaCl 2The TG-MS spectrogram of compound system.
Fig. 5 is LiBH 4NH 3With mesoporous SiO 2The TG-MS spectrogram of compound system.
Specific embodiments
Below in conjunction with specific embodiment, the present invention is further elaborated.Embodiment only is used for the present invention is done explanation rather than limitation of the present invention.
Embodiment 1:
Heating method prepares LiBH 4NH 3With MgCl 2Mixture
Under 25 ℃ of the room temperatures, with 0.5g LiBH 4NH 3With the super dried MgCl of 0.5g 2In argon gas, put in the Schlenk test tube.The test tube sealing is got in the air, and ultra-sonic dispersion took out product and is LiBH after 20 minutes in argon gas in 65 ℃ the aqueous solution 4NH 3With MgCl 2Mixture.Fig. 2 is the TG-MS spectrogram of this mixture.
Embodiment 2:
Prepared by Ball Milling LiBH 4NH 3With ZnCl 2Mixture
Under 10 ℃ of the room temperatures, with 0.5g LiBH 4NH 3With the super dried ZnCl of 0.5g 2Mix in ball grinder at argon gas.Ball grinder sealing back, is taken out in argon gas and is LiBH after 20 minutes with the 400 speed ball millings that change 4NH 3With ZnCl 2Mixture.Fig. 3 is the TG-MS spectrogram of this mixture.
Embodiment 3:
Heating method prepares LiBH 4NH 3With CaCl 2Mixture
Under 25 ℃ of the room temperatures, with 0.5g LiBH 4NH 3With the anhydrous CaCl of 0.5g 2In argon gas, put in the Schlenk test tube.Test tube sealing is got in the air, and ultra-sonic dispersion after 20 minutes in 65 ℃ the aqueous solution takes out product and to be LiBH in argon gas 4NH 3With CaCl 2Mixture.Fig. 4 is the TG-MS spectrogram of this mixture.
Embodiment 4:
Heating method prepares LiBH 4NH 3With SiO 2The mesoporous material mixture
Under 10 ℃ of the room temperatures, with 0.8g LiBH 4NH 3With the mesoporous SiO of 0.2g 2In argon gas, put in the Schlenk test tube.Test tube sealing is got in the air, 65 ℃ heated in water solution after 20 minutes, product taken out in argon gas be LiBH 4NH 3With mesoporous SiO 2Mixture.Fig. 5 is the TG-MS spectrogram of this mixture.
Embodiment 5:
LiBH 4NH 3With NiCl 2Compound system
Under 10 ℃ of the room temperatures, in argon gas, get 0.3g LiBH 4NH 3With 0.17g NiCl 2After the mixing, leave standstill the reaction that release hydrogen was promptly arranged after the several seconds and take place.

Claims (16)

1. one kind is the method that hydrogen source is produced hydrogen with the hydroborates ammonia complex, it is characterized in that with the hydroborates ammonia complex with put hydrogen promotor and mix back ball milling or heating, mix the compound hydrogen system of putting of preparation, will be compound put hydrogen system and heat release hydrogen.
2. method according to claim 1 is characterized in that the compound of hydroborates for carrying out complexing with ammonia in the described hydroborates ammonia complex; Ammonia complex M (BH wherein 4) nXNH 3All stable ammonia complexs for described hydroborates.
3. method according to claim 2 is characterized in that described hydroborates is selected from LiBH 4, Ca (BH 4) 2, Mg (BH 4) 2, Zn (BH 4) 2, Be (BH 4) 2Or Ni (BH 4) 2Described ammonia complex M (BH 4) nXNH 3Be LiBH 4XNH 3Or Mg (BH 4) 2XNH 3
4. method according to claim 1, it is characterized in that described put hydrogen promotor for can with one or more mixture of the ammonia complex of the material of ammonia generation complexing action, such material and mesoporous material.
5. method according to claim 4 is characterized in that the described material of putting in the hydrogen promotor with ammonia generation complexing is selected from Zn 2+, Ca 2+, Mg 2+, Cu 2+, Ni 2+Or Li 2+Muriate, hydrosulfate, fluorochemical, hydride or hydroborate.
6. method according to claim 4 is characterized in that describedly putting that mesoporous material is selected from iO in the hydrogen promotor 2, CNT (carbon nano-tube), BN nanotube, molecular sieve or mould material.
7. method according to claim 6 is characterized in that described mesoporous material uses separately or uses jointly with the Ammonia complex compound.
8. method according to claim 1 is characterized in that, when promotor is ammonia complex matter, with compound employing ball milled of hydroborates ammonia complex or heating method; When promotor is that mesoporous material, hydroborates ammonia complex are LiBH 4XNH 3The time, its compound employing heating method.
9. method according to claim 1 is characterized in that, the process that promotor and hydroborates ammonia complex is mixed with mixture is to carry out under the atmosphere of anhydrous and oxygen-free.
10. method according to claim 1 is characterized in that the ball milling time is no less than 5 minutes when with ball milled promotor being mixed with the hydroborates ammonia complex, and the ball milling temperature is not higher than the decomposition temperature of used material.
11. method according to claim 1, when it is characterized in that with the heating method mixing raw material, Heating temperature is between the fusing point and decomposition temperature of used hydroborates ammonia complex, and decomposition temperature is lower than the material of fusing point can not use heating method; Should stir in the heat-processed, or carry out ultra-sonic dispersion.
12. method according to claim 1 is characterized in that the weight ratio of described promotor and hydroborates ammonia complex is not less than 1: 10.
13. method according to claim 1 is characterized in that, heat prepared compound system in the described method and make its release hydrogen in rare gas element and vacuum, or heating is emitted hydrogen in air.
14. method according to claim 1 is characterized in that the initial hydrogen discharging temperature for preparing the gained mixture is lower than 100 ℃, kind and the consumption control by regulating promotor of the temperature of described initial release hydrogen and speed.
15. method according to claim 1 is characterized in that the hydrogen desorption capacity of described mixture is realized by the kind consumption of regulating promotor.
16. method according to claim 1 is characterized in that described promotor is hydroborate and ammonia complex thereof.
CN200910047260A 2009-03-09 2009-03-09 Method for preparing hydrogen by taking boron hydride ammino complex as hydrogen source Pending CN101830431A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102442646A (en) * 2010-10-13 2012-05-09 中国科学院大连化学物理研究所 High-capacity composite hydrogen storage material and hydrogen discharge method
CN102602889A (en) * 2012-03-15 2012-07-25 复旦大学 Novel and high-efficiency method for preparing ammonia-complex vanadium hydroboron of hydrogen storage system
CN103011078A (en) * 2012-11-28 2013-04-03 复旦大学 Preparation method and application of novel and efficient metal B-N-H system hydrogen storage material

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102442646A (en) * 2010-10-13 2012-05-09 中国科学院大连化学物理研究所 High-capacity composite hydrogen storage material and hydrogen discharge method
CN102602889A (en) * 2012-03-15 2012-07-25 复旦大学 Novel and high-efficiency method for preparing ammonia-complex vanadium hydroboron of hydrogen storage system
CN103011078A (en) * 2012-11-28 2013-04-03 复旦大学 Preparation method and application of novel and efficient metal B-N-H system hydrogen storage material

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Open date: 20100915