CN102659079A - Solid-phase synthesis method for magnesium borohydride ammoniates - Google Patents
Solid-phase synthesis method for magnesium borohydride ammoniates Download PDFInfo
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- CN102659079A CN102659079A CN2012101573730A CN201210157373A CN102659079A CN 102659079 A CN102659079 A CN 102659079A CN 2012101573730 A CN2012101573730 A CN 2012101573730A CN 201210157373 A CN201210157373 A CN 201210157373A CN 102659079 A CN102659079 A CN 102659079A
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- ammino
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Abstract
The invention discloses a solid-phase synthesis method for magnesium borohydride ammoniates. The solid-phase synthesis method comprises the following step of: performing ball milling on magnesium borohydride and an ammonia source under the atmosphere of protective gas to obtain the magnesium borohydride ammoniate. According to the solid-phase synthesis method for the magnesium borohydride ammoniates, the complicated operation processes of filtration, distillation and solvent removal in traditional methods are avoided, and the problem that organic waste liquid needs to be specially treated is solved; the product yield is increased; a series of magnesium borohydride ammoniates with different ammonia complexing numbers can be prepared; the operation is simple; the product purity is high; the yields of the magnesium borohydride ammoniates are respectively higher than 95 percent; the dehydriding temperature of the obtained product is about 130 DEG C; and the hydrogen discharge amount is higher than 13 weight percent (wt%).
Description
Technical field
The present invention relates to the preparation of hydrogen storage material, be specifically related to a kind of solid phase synthesis process of magnesium borohydride ammonate hydrogen storage material.
Background technology
The magnesium borohydride ammonate has the big (> 13wt% of hydrogen-storage amount), hydrogen discharging temperature is low, to advantages such as oxygen are insensitive, in the hydrogen as energy source utilization, is widely used, be one of research focus of present hydrogen storage material.
At present, mainly contain with ammonia and magnesium borohydride diethyl ether solution prepared in reaction six ammino magnesium borohydride, six ammino magnesium borohydride for magnesium borohydride ammonate compound method in the world and decompose preparation two ammino magnesium borohydride and in benzene and ether, use magnesium borohydride and ammonia gas react to generate two ammino magnesium borohydride and three ammino magnesium borohydride etc. respectively near stoichiometric ratio.
Preparing six ammino magnesium borohydride with ammonia and magnesium borohydride diethyl ether solution is the diethyl ether solutions that excessive dry ammonia fed magnesium borohydride, filters the extracting waste deposition then, under vacuum, adds the unnecessary ether of heat extraction and obtains six ammino magnesium borohydride.
From ammonia and magnesium borohydride diethyl ether solution preparation six ammino magnesium borohydride; Although the magnesium borohydride diethyl ether solution that can use Peng Qinghuana and magnesium chloride in ether, to react to make is as raw material; Avoided the preparation process of loaded down with trivial details relatively magnesium borohydride; Yet this method relates to operations such as filtration, solvent wash and vacuum-drying, is unfavorable in industrial production, promoting; And inevitably containing the certain amount of solvent ether in the six ammino magnesium borohydride that make of this method, degree of purity of production is restricted.
It is that six ammino magnesium borohydride are remained under certain temperature (100 ° of C) and the dynamic vacuum that six ammino magnesium borohydride are decomposed preparation two ammino magnesium borohydride; Decomposition reaction through six ammino magnesium borohydride makes per molecule six ammino magnesium borohydride lose four molecules of ammonia, thereby makes two ammino magnesium borohydride.
From six ammino magnesium borohydride, obtain the method for two ammino magnesium borohydride through thermal degradation, though can obtain two higher ammino magnesium borohydride of purity; But in this preparation process, sample is liquid under holding temperature (100 ° of C); And be cooled to be solidified as solid behind the normal temperature; This will cause sample preparation loaded down with trivial details, influence productive rate, limit the mass preparation of two ammino magnesium hydrides simultaneously
Under normal temperature (25 ° of C), in the benzole soln that contains excessive magnesium borohydride etherate, feed the ammonia of 90-95% stoichiometric ratio, can obtain two ammino magnesium borohydride.Under identical temperature, in the diethyl ether solution of magnesium borohydride, feed the ammonia of 90-95% stoichiometric ratio, can obtain three ammino magnesium borohydride.For above-mentioned two synthetic routes, all need use operations such as filtration and solvent wash to remove remaining magnesium borohydride ether adducts, carry out vacuum-drying afterwards at normal temperatures.
Use magnesium borohydride etherate and the ammonia that is slightly less than stoichiometric ratio in benzene or diethyl ether solution, to react, can prepare the two ammino magnesium borohydride and the three ammino magnesium borohydride of certain purity.But benzene that uses in this reaction scheme and ether have certain toxicity, and benzene is a kind of carcinogenic substance.In addition this synthetic route also to filter, subsequent disposal such as solvent wash and vacuum-drying, be unfavorable for large-scale promotion.This method needs the liquid magnesium borohydride etherate of accurately control and the amount of gasiform ammonia simultaneously, and this is difficult the realization in industrial production, can cause production cost to rise.
In addition; The method of existing synthetic magnesium borohydride ammonate only can be synthesized two ammino magnesium borohydride, three ammino magnesium borohydride and six ammino magnesium borohydride; Ammino closes also Shang Weiyou report of compound method that number is not equal to two, three or six magnesium borohydride ammonate, has restricted the magnesium borohydride ammonate as the application of hydrogen storage material in hydrogen storage system.
In sum; It is several controlled that existing magnesium borohydride ammonate preparation method is difficult to realize that ammino closes; And all there be low, the operational difficulty not high of productive rate in the preparation process, be unfavorable for problem such as scale operation with purity; Can not satisfy its application, therefore, need that a kind of simple, ammino of exploitation closes that number is controlled, purity and the higher magnesium borohydride ammonate preparation method of productive rate as hydrogen storage material.
Summary of the invention
The invention provides a kind of solid phase synthesis process of magnesium borohydride ammonate, simple to operate, it is controlled that ammino closes number, and productive rate and product purity are high.
A kind of solid phase synthesis process of magnesium borohydride ammonate comprises the steps: that under shielding gas atmosphere ball milling magnesium borohydride and ammonia source obtain the magnesium borohydride ammonate.
Described shielding gas is an ammonia, and the double described ammonia source of doing of this ammonia.
Ball milling temperature of the present invention does not have particular requirement, if no special instructions, all carries out at normal temperatures; Magnesium borohydride and ammonia or magnesium borohydride and six ammino magnesium borohydride react under mechanical force; Generate the magnesium borohydride ammonate, simple to operate, be fit to scale operation.
As preferably, the mol ratio of described magnesium borohydride and ammonia is 1:1 ~ 6.
Further preferred, the mol ratio of described magnesium borohydride and ammonia is 1:1,1:2,1:3,1:4,1:5 or 1:6.
Through changing the mol ratio of magnesium borohydride and ammonia, can obtain ammino and close the different a series of magnesium borohydride ammonates of number, control method is simple, and is easy to operate.
Described shielding gas is a rare gas element, and described ammonia source is six ammino magnesium borohydride.
As preferably, the mol ratio of described magnesium borohydride and six ammino magnesium borohydride is 1:0.2 ~ 5.
Further preferred, the mol ratio of described magnesium borohydride and six ammino magnesium borohydride is 5:1,2:1,1:1,1:2 or 1:5.
Mol ratio through magnesium borohydride and six ammino magnesium borohydride in the mixture that changes magnesium borohydride and six ammino magnesium borohydride; Can obtain ammino and close the different a series of magnesium borohydride ammonates of number; An ammino magnesium borohydride that has obtained to prepare among the existing preparation method, four ammino magnesium borohydride and five ammino magnesium borohydride; Control method is simple, has expanded the selectable range of magnesium borohydride ammonate as hydrogen storage material.
As preferably, described ammonia pressure is 0.5 ~ 10 normal atmosphere.
Ammonia pressure will influence under mechanical force, and ammino closes number in the speed of response of ammonia and magnesium borohydride and the product, and ammonia pressure is low excessively, the slow and magnesium borohydride ammonate purity drop that generates of speed of response then, and ammonia pressure can not surpass the ball grinder bearing capacity.
As preferably, described rare gas element is argon gas or nitrogen, and described inert gas pressure is 1 ~ 5 normal atmosphere.
Rare gas element is not participated in reaction, guarantees that the reaction of magnesium borohydride and six ammino magnesium borohydride generates the influence that the magnesium borohydride ammonate does not receive foreign gas, improves product gas purity.
Described ball milling condition is: ball-to-powder weight ratio 30 ~ 120:1, rotational speed of ball-mill 300 ~ 550rpm, ball milling time 24 ~ 96h.
Ball-to-powder weight ratio is too small, and grinding efficiency is low, and ball-to-powder weight ratio is excessive; Then power consumption is big, and the ball milling loss rate is high, suitable ball-to-powder weight ratio; Can guarantee the efficient of grinding, give full play to the impact grinding effect of ball, rotational speed of ball-mill and ball milling time will influence efficient, productive rate and the product gas purity of reaction.
Under protection of ammonia, the ball milling magnesium borohydride is when ball-to-powder weight ratio is 30 ~ 120:1; Rotational speed of ball-mill is 300 ~ 550rpm; The ball milling time carries out X-ray diffraction to the product that obtains and characterizes (XRD) when being 18 ~ 96h, and the result shows; Through the ball milling condition mole when of adjustment magnesium borohydride and ammonia, can prepare purity and close several magnesium borohydride ammonates greater than 96% different amminos.
Under protection of inert gas; Magnesium borohydride and six ammino magnesium borohydride mol ratios are respectively 5:1,2:1,1:1,1:2,1:5, and when ball-to-powder weight ratio is 30 ~ 120:1, rotational speed of ball-mill is 300 ~ 550rpm; The ball milling time is when being 18 ~ 96h; The product that obtains is carried out XRD respectively characterize, the result shows that the product for preparing all has and only have a kind of characteristic diffraction peak of magnesium borohydride ammonate; Be respectively an ammino magnesium borohydride, two ammino magnesium borohydride, three ammino magnesium borohydride, four ammino magnesium borohydride and five ammino magnesium borohydride, explain that what prepare all is highly purified magnesium borohydride ammonate.
Magnesium borohydride ammonate compound method provided by the invention complex operations process and organic liquid waste such as has been avoided filtering in the existing method, distill, desolvate and has been needed problems such as special disposal, has improved the productive rate of product; Can prepare a series of amminos and close the different magnesium borohydride ammonate of number; Simple to operate, product purity is high, and productive rate is all more than 95%; The hydrogen discharging temperature of products therefrom is about 130 ℃, and hydrogen desorption capacity is more than 13wt%.
Description of drawings
Fig. 1 is the six ammino magnesium borohydride XRD figures spectrum of the embodiment of the invention 1 preparation;
Fig. 2 is the ammino magnesium borohydride XRD figure spectrum of the embodiment of the invention 2 preparations;
Fig. 3 is the two ammino magnesium borohydride XRD figures spectrum of the embodiment of the invention 3 preparations;
Fig. 4 is the three ammino magnesium borohydride XRD figures spectrum of the embodiment of the invention 4 preparations;
Fig. 5 is that the volume of three ammino magnesium borohydride of the embodiment of the invention 4 preparations is put the hydrogen curve.
Embodiment
Embodiment 1
In glove box, with Mg (BH
4)
2Pack into can seal, the stainless steel jar mill of belt switch valve, after ball grinder vacuumized, charged pressure be 10 normal atmosphere (among the present invention if no special instructions; The accurate normal atmosphere of the equal index of normal atmosphere) ammonia, under ammonia atmosphere, ball milling on planetary ball mill; Ball-to-powder weight ratio is 120:1, and rotating speed is 300rpm, and the ball milling time is 36h; After ball milling finishes, product is carried out XRD test (XRD of sample measures) on X ' the Pert Pro X-ray diffractometer of Philip.
Fig. 1 is the XRD figure spectrum of product, and product has and only have the characteristic diffraction peak of six ammino magnesium borohydride.
Embodiment 2
Prepare the magnesium borohydride ammonate by embodiment 1 said method, the preparation condition difference is seen table 1.
After having prepared, product is weighed, calculate that the magnesium borohydride ammino closes number in the product, table 1 has been listed the ratio that product weight increases and the kind of product.The result finds, through changing preparation condition, can obtain an ammino magnesium borohydride, two ammino magnesium borohydride, three ammino magnesium borohydride, four ammino magnesium borohydride and five ammino magnesium borohydride respectively.
The experiment condition of ball milling magnesium borohydride and product under table 1 ammonia atmosphere
In glove box, with Mg (BH
4)
2And Mg (BH
4)
26NH
3According to the mixed in molar ratio of 5:1, pack into can seal, the stainless steel jar mill of belt switch valve, under 1 normal atmosphere argon gas atmosphere, ball milling on planetary ball mill, ball-to-powder weight ratio is 60:1, rotating speed is 550rpm, the ball milling time is 18h.After ball milling finishes, product is carried out the XRD test.
Fig. 2 is the XRD figure spectrum of product, and product has and only have the characteristic diffraction peak of an ammino magnesium borohydride.
Embodiment 4
In glove box, with Mg (BH
4)
2And Mg (BH
4)
26NH
3According to the mixed in molar ratio of 2:1, pack into can seal, the stainless steel jar mill of belt switch valve, under 1 normal atmosphere argon gas atmosphere, ball milling on planetary ball mill, ball-to-powder weight ratio is 80:1, rotating speed is 300rpm, the ball milling time is 96h.After ball milling finishes, product is carried out the XRD test.
Fig. 3 is the XRD figure spectrum of product, and product has and only have the characteristic diffraction peak of two ammino magnesium borohydride.
Embodiment 5
In glove box, with Mg (BH
4)
2And Mg (BH
4)
26NH
3According to the mixed in molar ratio of 1:1, pack into can seal, the stainless steel jar mill of belt switch valve, under 1 normal atmosphere nitrogen atmosphere, ball milling on planetary ball mill, ball-to-powder weight ratio is 30:1, rotating speed is 400rpm, the ball milling time is 48h.After ball milling finishes, product is carried out the XRD test.
Fig. 3 is the XRD figure spectrum of product, and product has and only have the characteristic diffraction peak of three ammino magnesium borohydride.
Hydrogen discharging performance to product is tested; Test is carried out on gaseous state hydrogen discharging performance testing apparatus; Before the test; Reactive system vacuumizes earlier, puts hydrogen process service routine temperature controller control heating rate and temperature, and hydrogen pressure, program temperature and the thermopair observed temperature of automatic record reactive system are over time in the experimentation.
The hydrogen discharging temperature of all products is between 130 ~ 450 ° of C, and hydrogen desorption capacity is more than 13wt%.
Fig. 5 is put the hydrogen curve for the volume of product.Can find out that the initial hydrogen discharging temperature of product is at 130 ° of C, hydrogen desorption capacity is about 14wt%.
Claims (10)
1. the solid phase synthesis process of a magnesium borohydride ammonate is characterized in that, comprises the steps: under shielding gas atmosphere, and ball milling magnesium borohydride and ammonia source obtain the magnesium borohydride ammonate.
2. magnesium borohydride solid phase synthesis process as claimed in claim 1 is characterized in that, described shielding gas is an ammonia, and the double described ammonia source of doing of this ammonia.
3. magnesium borohydride solid phase synthesis process as claimed in claim 2 is characterized in that, the mol ratio of described magnesium borohydride and ammonia is 1:1 ~ 6.
4. magnesium borohydride solid phase synthesis process as claimed in claim 3 is characterized in that, the mol ratio of described magnesium borohydride and ammonia is 1:1,1:2,1:3,1:4,1:5 or 1:6.
5. magnesium borohydride solid phase synthesis process as claimed in claim 1 is characterized in that, described shielding gas is a rare gas element, and described ammonia source is six ammino magnesium borohydride.
6. magnesium borohydride solid phase synthesis process as claimed in claim 5 is characterized in that, the mol ratio of described magnesium borohydride and six ammino magnesium borohydride is 1:0.2 ~ 5.
7. magnesium borohydride solid phase synthesis process as claimed in claim 6 is characterized in that, the mol ratio of described magnesium borohydride and six ammino magnesium borohydride is 5:1,2:1,1:1,1:2 or 1:5.
8. magnesium borohydride solid phase synthesis process as claimed in claim 2 is characterized in that, described ammonia pressure is 0.5 ~ 10 normal atmosphere.
9. magnesium borohydride solid phase synthesis process as claimed in claim 5 is characterized in that, described rare gas element is argon gas or nitrogen, and inert gas pressure is 1 ~ 5 normal atmosphere.
10. magnesium borohydride solid phase synthesis process as claimed in claim 1 is characterized in that, described ball milling condition is: ball-to-powder weight ratio 30 ~ 120:1, rotational speed of ball-mill 300 ~ 550rpm, ball milling time 18 ~ 96h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591089A (en) * | 2015-01-09 | 2015-05-06 | 浙江大学 | Preparation method of nano-particle type borohydride ammonate |
| CN107758611A (en) * | 2017-10-31 | 2018-03-06 | 常州富思通管道有限公司 | A kind of magnesium-base nanometer composite hydrogen-storing material and preparation method thereof |
| EP3624247A1 (en) * | 2018-09-14 | 2020-03-18 | Aarhus Universitet | A fast ionic conductor with stoichiometry mg(bh4)2·xnh3 |
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| CN101746727A (en) * | 2008-12-08 | 2010-06-23 | 复旦大学 | Method for preparing LiBH4 xNH3 compounds |
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| 《Inorganic Chemistry》 20080423 Grigorii Soloveichik et al. "Ammine Magnesium Borohydride Complex as a New Material for Hydrogen Storage: Structure and Properties of Mg(BH4)2•2NH3" 第4290－4298页 1-10 第47卷, 第10期 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591089A (en) * | 2015-01-09 | 2015-05-06 | 浙江大学 | Preparation method of nano-particle type borohydride ammonate |
| CN107758611A (en) * | 2017-10-31 | 2018-03-06 | 常州富思通管道有限公司 | A kind of magnesium-base nanometer composite hydrogen-storing material and preparation method thereof |
| EP3624247A1 (en) * | 2018-09-14 | 2020-03-18 | Aarhus Universitet | A fast ionic conductor with stoichiometry mg(bh4)2·xnh3 |
| WO2020053423A1 (en) | 2018-09-14 | 2020-03-19 | Aarhus Universitet | A fast ionic conductor with stoichiometry mg(bh4)2·xnh3 |
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