CN103303867A - Method for synthesizing ammonia borane - Google Patents
Method for synthesizing ammonia borane Download PDFInfo
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- CN103303867A CN103303867A CN2013102852285A CN201310285228A CN103303867A CN 103303867 A CN103303867 A CN 103303867A CN 2013102852285 A CN2013102852285 A CN 2013102852285A CN 201310285228 A CN201310285228 A CN 201310285228A CN 103303867 A CN103303867 A CN 103303867A
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- ammonia borine
- dioxane
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- sodium borohydride
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Abstract
The invention discloses a method for synthesizing ammonia borane. The method comprises the following two synthesizing steps of: 1, reacting a mixture of ammonium fluoroborate and sodium borohydride in an experimental container with a reflux unit in which a dioxane solvent is filled, thereby obtaining a dioxane solvent for dissolving ammonia borane; 2, performing heating and spin drying treatment on the solvent by utilizing a rotary evaporator, thereby obtaining the product ammonia borane. In the process, the dioxane recovered by utilizing the rotary evaporator can be repeatedly utilized to serve as the solvent in the ammonia borane preparation process. In the method, the ammonium fluoroborate serves as an ammonium source for the first time, the synthetic method is simple, the product yield is considerable, and the purity is high.
Description
Technical field
Technical scheme of the present invention relates to a kind of method of simple, cheap synthetic chemistry hydrogen storage material ammonia borine.
Background technology
Ammonia borane compound (NH
3BH
3) be a kind of chemical hydride hydrogen storage material that obtains paying close attention to recent years.It contain hydrogen density up to 19.6wt.%, it has moderate thermostability and the good advantages such as chemical stability, is appealed very high expectation in on-board hydrogen energy source use field.Simultaneously, the product that process is put behind the hydrogen is the quite high boron nitride of purity (BN) stupalith, also causes people's close attention.
In recent years, considerable research worker be devoted to diverse ways and raw material prepare the ammonia borine work.Human lithium borohydride and the ammonium salts such as Shore are such as NH
4Cl, (NH
4)
2SO
4(NH
4)
2CO
3Synthetic ammonia borine (Shore, S.G.; Parry, R.W.J.Am.Chem.Soc.1955,77,6084).Subsequently the human sodium borohydride such as Hu and corresponding ammonium salt (NH
4Cl, (NH
4)
2SO
4(NH
4)
2CO
3) synthesized equally the ammonia borine.Mayer in 1973 etc. report a kind of new method, namely use diborane and ammino ammonification borine (Mayer, E.Inorg.Chem.1973,12,1954) in ethane.The report of Ramachandran in 2007 and Gagare summing-up utilize sodium borohydride and different ammonium salt (NH
4Cl, (NH
4)
2SO
4, (NH
4)
2CO
3, NH
4OAc, NH
4F, NH
4NO
3And NH
4HCO
3) method of synthetic ammonia borine, detailed description comprising purity and productive rate, and the different solvents that uses is on the impact of this purity and productive rate, this report explanation utilizes dioxane as solvent, the ammonia borine purity higher (98%) that ammonium sulfate obtains as the ammonium source, productive rate can reach 95%, and speed of reaction is very fast soon.But the common complex technical process of above preparation method, and cost is higher.
The present invention adopts cheap ammonium borofluoride and sodium borohydride respectively as ammonium source and boron source first, and adopts recycled dioxane successfully to prepare highly purified ammonia borine as solvent.The method can access the higher ammonia borine (95%) of productive rate, and ammonia borine purity height can reach (98%), and the reaction solvent dioxane can recycling.1100 ℃ of these ammonia borines of pyrolysis obtain purity and the higher boron nitride ceramic material of degree of crystallinity.This ammonia borine of catalytic hydrolysis produces the hydrogen of capacity, and the height that further specifies it is put the hydrogen characteristics.The simple and easy cheapness of this synthetic method, the ammonia borine purity that obtains is high, is a kind of novel method that can suitability for industrialized production ammonia borine.
Summary of the invention
Technical problem to be solved by this invention is: a kind of new ammonia borine synthetic method is provided, and the method cheap and simple, product yield is considerable, and purity is higher.Adopted for two steps synthetic: the first step, the mixture of ammonium borofluoride and sodium borohydride be equipped with the dioxane solvent with reflux experiment container internal reaction, obtain the dioxane solvent of dissolved ammonia borine; Second step utilizes Rotary Evaporators to be spin-dried for processing to what this solvent was heated, obtains ammonia borine product.In this process, the dioxane that utilizes Rotary Evaporators to reclaim can repeatedly be reused as the solvent in this preparation ammonia borine process.In the methods of the invention, use first ammonium borofluoride as the ammonium source, synthetic method is simple, and product yield is considerable, and purity is higher.
The present invention solves this technical problem the technical scheme that adopts:
A kind of synthetic method of ammonia borine the steps include:
(1) ammonium borofluoride and sodium borohydride are put into the reactor with reflux that fills solvent, then the mixing solutions of the ammonium borofluoride-sodium borohydride of system-solvent is heated stirring reaction 1-20 hour, and temperature of reaction is 30-80 ℃; Wherein, mol ratio is ammonium borofluoride: sodium borohydride=0.5～2:1, and the amount of ammonium borofluoride and sodium borohydride sum is 0.05～0.2g/ml in the solvent;
(2) mixing solutions that obtains through reaction in the suction filtration step (1) obtains clear solution;
(3) with the clear solution that obtains in the step (2) at 50-80 ℃ of lower rotary evaporation, obtaining white lightweight sample is the ammonia borine; Revolve the solvent that steams and can be used as the solvent cycle utilization of lower secondary response.
Solvent for use is dioxane, or through dioxane that recycle, that in front preparation ammonia borine process, be evaporated.
The invention has the beneficial effects as follows:
1. the resulting product of the inventive method is the higher ammonia borine product of purity.Corresponding one by one with the standard diffraction data of ammonia borine through the diffraction peak that accurate indexing (XRD) collection of illustrative plates draws, illustrate that it has higher purity and degree of crystallinity.Obtain high-purity ammonia borine product by the contrast infared spectrum.The by product of this experiment is pure Sodium tetrafluoroborate (NaBF
4).Because the ammonia borine can be dissolved in the dioxane solvent, and Sodium tetrafluoroborate is insoluble to the dioxane solvent, so can realize fully and the separating of by product by simple filtration or suction filtration, at last by being spin-dried for the solvent of this separation, obtain high-purity ammonia borine product.Utilize simultaneously the recuperable dioxane solvent of Rotary Evaporators, the dioxane solvent of this recovery can reuse, and again obtains high-purity ammonia borine product.As presoma, can obtain high-purity boron nitride ceramic material with this ammonia borine.What this ammonia borine of catalysis can obtain capacity fast puts the hydrogen effect, shows the hydrogen storage material that this ammonia borine is a kind of character excellence.
2. the raw material that adopts of the present invention is ammonium borofluoride and sodium borohydride, all belongs to the general chemical starting material of suitability for industrialized production, and is cheap and easy to get, nontoxic, and choosing of ammonium borofluoride particularly reduced the cost of product.
Present method synthetic the ammonia borine have the characteristics of high purity, high crystalline.This preparation process cheap and simple can realize scale operation.
4. the dioxane solvent can be crossed repeatedly and recycles among the present invention, saves solvent load, has reached cheap synthetic effect.
Description of drawings
The present invention is further described below in conjunction with accompanying drawing and implementation.
Fig. 1 is the XRD spectra of ammonia borine in the example 1.
Fig. 2 is the XRD spectra of by product in the example 1.
Fig. 3 is the FTIR spectrogram of ammonia borine product in the example 1.
Fig. 4 is the XRD spectra of the ammonia borine product that obtains as solvent of the dioxane of ten recycles in the example 1.
Fig. 5 be with the ammonia borine in the example 1 as presoma, boron nitride XRD figure that pyrolysis obtains spectrum.
Fig. 6 for the ammonia borine in the example 1 as putting the hydrogen material, the properties amount is along with the variation diagram of time in water.
Embodiment
Embodiment 1
(1) 26.21g ammonium borofluoride and 9.46g sodium borohydride (molar ratio of ammonium borofluoride and sodium borohydride is 1) are put into the reactor with reflux that fills 250 milliliters of dioxane solvents, ammonium borofluoride-the sodium borohydride of system-dioxane mixing solutions, then be heated stirring reaction at least 10 hours, Heating temperature is 40 ℃;
(2) mixing solutions that obtains through reaction in the suction filtration step (1) obtains clear solution;
(3) with the clear solution that obtains in the step (2) at 70 ℃ of lower rotary evaporations, obtain white lightweight sample, be the ammonia borine;
X-ray diffraction (XRD) collection of illustrative plates of product as shown in Figure 1, in the angle of diffraction scope of measuring, each diffraction peak is all very clear, sharp-pointed, corresponding one by one with the standard diffraction data of ammonia borine through the diffraction peak that accurate indexing (XRD) collection of illustrative plates draws, illustrate that it has higher purity and degree of crystallinity.The diffraction peak that does not have other dephasigns in the XRD figure.Be illustrated in figure 2 as the XRD figure spectrum of the by product of compound experiment.The by product of this experiment is pure Sodium tetrafluoroborate (NaBF
4), can infer that therefore the synthetic chemistry reaction belongs to typical substitution reaction, i.e. NH
4BF
4+ NaBH
4→ NH
4BH
4+ NaBF
4, during reaction there is a large amount of hydrogen to produce, illustrate that further dehydrogenation reaction, i.e. NH occur the product ammonium borohydride
4BH
4→ NH
3BH
3+ H
2↑.Because the ammonia borine can be dissolved in the dioxane solvent, and Sodium tetrafluoroborate is insoluble to the dioxane solvent, so can realize fully and the separating of by product by simple filtration or suction filtration, at last by being spin-dried for the solvent of this separation, obtain high-purity ammonia borine product.Shown in Figure 3 is the Fourier transform infrared spectrum (FTIR) of the ammonia borine sample of preparation.This infared spectrum illustrates that this ammonia borine that obtains has high-purity characteristics, namely belongs to the typical intramolecule key chattering of ammonia borine except several, does not have to find to belong to the vibration peak of other impurity, illustrates that the purity of this synthetic ammonia borine is more than 95%.
Change step (1) ammonium borofluoride among the embodiment 1 into 13.11g and 52.42g (molar ratio of ammonium borofluoride and sodium borohydride is respectively 0.5 and 2), other operations is all identical with embodiment 1, obtains product with embodiment 1.
Embodiment 4, example 5
The molar ratio that the consumption of step (1) sodium borohydride among the embodiment 1 is changed respectively into 4.73g and 18.92g(ammonium borofluoride and sodium borohydride is respectively 2 and 0.5), other operations is all identical with embodiment 1, obtains product with embodiment 1.
Embodiment 6
Dioxane in the step (1) among the embodiment 1 divided change 500ml into, other operations is all identical with embodiment 1, obtains product with embodiment 1.
Embodiment 7
Change the heated and stirred temperature of step (1) among the embodiment 1 into 60 ℃, other operations is all identical with embodiment 1, obtains product with embodiment 1.
Change respectively the operant response time of step (1) among the embodiment 1 into 1h and 48h, other operations is all identical with embodiment 1, obtains product with embodiment 1.
The operation of step (2) among the embodiment 1 is spin-dried for temperature changes respectively 50 ℃ and 80 ℃ into, other operations is all identical with embodiment 1, obtains product with embodiment 1.
Embodiment 12
The waste liquid that rotary evaporation in the step (3) among the embodiment 1 is obtained serves as the solvent of step among the embodiment 1 (1) again, and other operations is all identical with embodiment 1, obtains product with embodiment 1.
Embodiment 13
The waste liquid that rotary evaporation in the step (3) among the embodiment 1 is obtained serves as the solvent of step among the embodiment 1 (1) the tenth time, and other operations is all identical with embodiment 1, obtains product with embodiment 1.
Shown in Figure 4 is take through the XRD figure spectrum of the dioxane behind ten cycling and reutilizations as the ammonia borine product of solvent preparation, and product still has higher purity and degree of crystallinity (98%).
Embodiment 14
The 1100 ℃ of processing under argon gas atmosphere of product in the step (3) among the embodiment 1 are obtained white product.
As presoma, the lower 1100 ℃ of pyrolysis of argon gas atmosphere obtain purity and the higher boron nitride ceramic material of degree of crystallinity to this ammonia borine with this synthetic ammonia borine, and the XRD figure spectrum of product as shown in Figure 5.
Embodiment 15
Product in the step (3) among the embodiment 1 is hydrolyzed under the effect of NiBN composite catalyst, collects the hydrogen of emitting, and the speed of putting hydrogen by the gas chromatograph analysis.Fig. 6 is hydrolyzed the rate diagram of putting hydrogen for the ammonia borine product of preparation under the effect of NiBN composite catalyst.As shown in the figure, the ammonia borine that the above step of NiBN catalytic hydrolysis 0.021g is synthetic is put hydrogen volume near 47 milliliters for the first time, illustrates that this ammonia borine has higher purity, higher hydrogen discharging rate and enough hydrogen desorption capacities also show the hydrogen storage material that this ammonia borine is a kind of character excellence.
Claims (2)
1. the synthetic method of an ammonia borine is characterized by and comprises the steps:
(1) ammonium borofluoride and sodium borohydride are put into the reactor with reflux that fills solvent, then the mixing solutions of the ammonium borofluoride-sodium borohydride of system-solvent is heated stirring reaction 1-20 hour, and temperature of reaction is 30-80 ℃; Wherein, mol ratio ammonium borofluoride: sodium borohydride=0.5-2:1, the amount of ammonium borofluoride and sodium borohydride sum is 0.05～0.2g/ml in the solvent;
(2) mixing solutions that obtains through reaction in the suction filtration step (1) obtains clear solution;
(3) with the clear solution that obtains in the step (2) at 50-80 ℃ of lower rotary evaporation, obtaining white lightweight sample is the ammonia borine; Revolve the solvent that steams as the solvent cycle utilization of lower secondary response.
2. the synthetic method of ammonia borine as claimed in claim 1, it is characterized by solvent for use is dioxane, or the dioxane through recycling, be evaporated in preparation ammonia borine process.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103569967A (en) * | 2013-11-18 | 2014-02-12 | 复旦大学 | Preparation method of ammonia borane (NH3BH3) |
| CN104386657A (en) * | 2014-11-12 | 2015-03-04 | 河北工业大学 | Preparation method of high-crystallinity boron nitride |
| CN104445109A (en) * | 2014-11-12 | 2015-03-25 | 河北工业大学 | Method for assisted synthesis of high-crystallization boron nitride by utilizing surfactant |
| CN104630819A (en) * | 2015-02-10 | 2015-05-20 | 河南科技大学 | Process method for preparing ammonia borane from boroxol acid ammonium through electrochemical reduction in recycling manner |
| KR101568142B1 (en) * | 2013-10-16 | 2015-11-11 | (주)원익머트리얼즈 | Continuous system for producing ammonia borane and method of producing ammonia borane using the same |
| CN109052343A (en) * | 2018-10-08 | 2018-12-21 | 河北工业大学 | A kind of preparation method of ultra-thin hexagonal boron nitride piece |
| CN112158815A (en) * | 2020-11-03 | 2021-01-01 | 吉林大学 | Synthesis method of hydrazine borane |
| CN115652428A (en) * | 2022-12-02 | 2023-01-31 | 中国科学院福建物质结构研究所 | Nonlinear optical crystal NH 3 BH 3 And its preparation method and application |
-
2013
- 2013-07-09 CN CN2013102852285A patent/CN103303867A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| P.VEERARAGHAVAN RAMACHANDRAN ET. AL.: "Preparation of Ammonia Borane in High Yield and Purity, Methanolysis, and Regeneration", 《INORGANIC CHEMISTRY》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101568142B1 (en) * | 2013-10-16 | 2015-11-11 | (주)원익머트리얼즈 | Continuous system for producing ammonia borane and method of producing ammonia borane using the same |
| CN103569967A (en) * | 2013-11-18 | 2014-02-12 | 复旦大学 | Preparation method of ammonia borane (NH3BH3) |
| CN103569967B (en) * | 2013-11-18 | 2015-10-28 | 复旦大学 | A kind of preparation method of ammonia borine |
| CN104386657A (en) * | 2014-11-12 | 2015-03-04 | 河北工业大学 | Preparation method of high-crystallinity boron nitride |
| CN104445109A (en) * | 2014-11-12 | 2015-03-25 | 河北工业大学 | Method for assisted synthesis of high-crystallization boron nitride by utilizing surfactant |
| CN104445109B (en) * | 2014-11-12 | 2016-08-24 | 河北工业大学 | A kind of method of surfactant auxiliary synthesis high-crystallinity boron nitride |
| CN104630819A (en) * | 2015-02-10 | 2015-05-20 | 河南科技大学 | Process method for preparing ammonia borane from boroxol acid ammonium through electrochemical reduction in recycling manner |
| CN104630819B (en) * | 2015-02-10 | 2017-04-12 | 河南科技大学 | Process method for preparing ammonia borane from boroxol acid ammonium through electrochemical reduction in recycling manner |
| CN109052343A (en) * | 2018-10-08 | 2018-12-21 | 河北工业大学 | A kind of preparation method of ultra-thin hexagonal boron nitride piece |
| CN112158815A (en) * | 2020-11-03 | 2021-01-01 | 吉林大学 | Synthesis method of hydrazine borane |
| CN115652428A (en) * | 2022-12-02 | 2023-01-31 | 中国科学院福建物质结构研究所 | Nonlinear optical crystal NH 3 BH 3 And its preparation method and application |
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Application publication date: 20130918 |