CN102530870A - Method for preparing ammonia borane by wet chemical process - Google Patents
Method for preparing ammonia borane by wet chemical process Download PDFInfo
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- CN102530870A CN102530870A CN2010106030286A CN201010603028A CN102530870A CN 102530870 A CN102530870 A CN 102530870A CN 2010106030286 A CN2010106030286 A CN 2010106030286A CN 201010603028 A CN201010603028 A CN 201010603028A CN 102530870 A CN102530870 A CN 102530870A
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Abstract
The invention provides a new method for preparing ammonia borane, which synthesizes ammonia borane with high efficiency by using an ammonium salt and a boron hydride as raw materials and an organic solvent as a reaction medium and by a wet chemical process. The method is characterized in that the chemical reaction between the starting raw materials is directly promoted by wet-process heating ball milling to form ammonia borane. Subsequently, ball milled pulp is subjected to centrifugal separation and reduced-pressure distillation, the clear liquid is obtained, and thus, high-purity ammonia borane crystal is obtained. The centrifugally separated and ball milled solid is subjected to multiple times of solvent extraction to achieve high yield.
Description
Technical field
The present invention relates to the technology of preparing of ammonia borine, be specially the efficient of a kind of ammonia borine of invention, low-cost preparation method.
Background technology
The ammonia borine is the most basic boron-nitrogen compound, and molecular formula is H
3NBH
3Its research is started from the fifties in last century the earliest, but owing to there not being suitable application background to cause research to stay cool.In recent years, along with the expansion day by day of global energy demand, the development and utilization of various emerging energies progressively obtained paying attention to.Wherein Hydrogen Energy is regarded as the important composition of 21 century new forms of energy structure as a kind of cleaning, safety, renewable energy source efficiently.Utilization to Hydrogen Energy need combine to produce hydrogen, the research and development of series of new techniques such as Chu Qing.One of future thrust of current automotive industry is exactly to research and develop the hydrogen fuel cell automobile, to realize the target of low carbon emission reduction.And complete day by day along with fuel cell technology, vehicle-mounted storage hydrogen (hydrogen source) system becomes main restricting factor, and each big motor corporation all drops into huge fund research and development novel hydrogen storage material for this reason.The ammonia borine has high hydrogen density (19.6wt%) in all hydrogeneous solids, and has ambient-temp-stable and advantage such as nontoxic concurrently, thereby is well suited for as the new chemical hydrogen storage material.Ammonia borine pyrolysis dehydrogenation relates to three-step reaction,
nNH
3BH
3→[NH
2BH
2]n+nH
2
[NH
2BH
2]n→[NHBH]n+nH
2
[NHBH]n→nBN+nH
2
Desired reaction temperature is respectively 110 ℃, and 150 ℃ and 300 ℃, all being higher than Proton Exchange Membrane Fuel Cells used heat institute can support temperature (＜100 ℃).In recent years, the research of ammonia borine hydrogen storage property is mainly concentrated on the following aspects, 1. improve its dehydrogenation kinetics in solution through adding catalyzer, katalysis mostly occurs in the first step dehydrogenation.2. support the ammonia borine in duct outer surface or hole, change its dehydrogenation thermodynamics by interacting with carrier surface.3. with ammonia borine and hydrogenate or amino-complex effect, synthesizing new ammonia borane derivative is realized complete chemical modification.The basic metal amido borane compound that synthesizes has at present shown very approaching practical hydrogen storage property, is one of focus of Chu Qing research.Many achievements of ammonia borine study on the modification are directly caused the increase of ammonia borine demand, and fancy price has then limited the broad research to it.With Sigma Aldrich is example, and the ammonia borine price of its sale is up to 150 yuan/g, and often is the name restrict sales of strategic material with the high energy material.Therefore, the high efficiency preparation method of research ammonia borine is used its storage hydrogen has very significance.The preparation method of ammonia borine mainly comprises borine method and hydroborate method.Borine method (shore method) is to be the boron source with the borine, at-78 ℃ of direct and liquid nitrogen effect generation ammonia borines.Consider that borine is a kind of inflammable and highly toxic substance, its production application danger close, thereby this method can be restricted in practical application.The hydroborate method is to be the boron source with the hydroborate, through acting on one-step synthesis ammonia borine with ammonium salt (like ammonium chloride, ammonium sulfate etc.).This method is owing to the employing poisonous material, and synthesis condition is gentle, and becomes the main stream approach of current synthetic ammonia borine.The effect of hydroborate and ammonium salt is many to be carried out in solution, because hydroborate is dissolvable in water many organic solvents, adopts wet chemistry method can increase reaction interface, improves reaction efficiency.Yet conventional solution stirring mode is helpless to reduce the ammonium salt granularity, and reaction can only slowly be carried out the erosion action on ammonium salt surface through solution, and reaction efficiency is low.As the ball-milling processing ammonium salt reduces granularity in advance, then increases one procedure again.In addition, the solubleness of hydroborate in solvent is limited, and reducing its granularity is to improve deliquescent prerequisite.
Summary of the invention
The objective of the invention is to develop ammonia borine preparation method efficiently.Particularly, through the wet chemical synthesis of temperature control ball milling, to realize low cost, synthesis of high purity ammonia borine product expeditiously is for its suitability for industrialized production is at home established technical foundation.
Method of the present invention is to adopt ammonium salt (comprising volatile salt, ammonium chloride, ammonium sulfate etc.), hydroborate (to comprise lithium borohydride; Peng Qinghuana etc.) be raw material; With organic solvent (comprising THF, ether etc.) is reaction medium, through the wet chemical method synthetic ammonia borine of temperature control ball milling.Concrete reaction process is (is example with volatile salt and Peng Qinghuana reaction),
(NH
4)
2CO
3+2NaBH
4→2NH
3BH
3+Na
2CO
3+2H
2
Owing to be reflected in the airtight ball grinder and carry out, thereby, can judge to react and carry out degree, avoid reacting not exclusively or overreaction through detecting the growing amount of hydrogen.The ball milling temperature is controlled at 45 ℃; Ball milling speed is 100rpm; Only the ball grinder internal pressure promptly reaches preset value (preset value refers to that by product is a hydrogen in the reaction process after 45 minutes; Amounts of hydrogen after the complete reaction can calculate through material quantity, can calculate the theoretical pressure value in the ball grinder after the complete reaction through The Ideal-Gas Equation) indicate that reaction process accomplishes.White slurry behind the ball milling goes out clear liquid through spinning, then utilizes the rotatory evaporator underpressure distillation to go out THF, obtains the crystallization of ammonia borine.But another advantage of this method is a large amount of reactants of single treatment, not limited by initial boron hydride dissolves degree.The white slurries in reaction back are ammonia borine supersaturated solution, still contain the ammonia borine in the solid after the centrifugal treating, so repeatedly extraction can improve product yield.
Temperature control ball milling synthetic ammonia borine proposed by the invention; Than conventional heated and stirred; Its outstanding advantage is that the steel ball in the ball grinder not only reduces being suspended in the initial thing particle diameter in the organic solvent through bump, grinding; Also play stirring action to increase the solid-liquid reaction interface, improve speed of reaction.
Description of drawings
Fig. 1. the process flow sheet of temperature control ball milling synthetic ammonia borine.(the ammonia borine is abbreviated as AB among the figure)
Fig. 2. the X-ray powder diffraction figure of ammonia borine product.
Embodiment
The present invention is through the direct synthetic ammonia borine of the mode of temperature control ball milling, and concrete synthesis flow is as shown in Figure 1, is example with volatile salt and Peng Qinghuana reaction.Other raw materials also adopt identical flow process.Below through implementing row the present invention is made detailed description, but the present invention is not limited to these embodiment.
Embodiment 1:
In the argon gas glove box, take by weighing 19 gram NaBH
4, 24.8 the gram (NH
4)
2CO
3(there have slightly to be excessive, to avoid NaBH
4Superfluous and be dissolved in THF and cause it to be difficult to separate with the ammonia borine), and measure 500 milliliters of THF.With three pack in the lump voluntarily (2 liters of volumes) in the ball grinder of design.Tank body is packed into after airtight planetary ball mill (Fischt PM-400) is accurately controlled the ball milling chambers temp in 45 ℃, and ball milling is 45 minutes under 100rpm.Ball grinder is connected with tensimeter, measures a jar internal pressure 128psi, calculating gained hydrogen amount by equation for ideal gases is 0.5mol, confirms to react fully and accomplishes.Hydrogen in the jar is discharged, shift out white slurry to 600 milliliter tophan pot.Centrifugal treating 15min under the 3000r/min rotating speed, gained clear liquid partly move in 1 liter of round-bottomed bottle, place the Rotary Evaporators underpressure distillation.Promptly get the crystallization of white ammonia borine after THF removes, take out and be weighed as 8.25 grams.Revolve and steam the THF collect and pour into once more in the centrifugal gained solid residue.Room-temperature ball-milling was handled 15 minutes under the 100rpm, and repeated centrifugation is revolved the steaming treating processes, and reextraction obtains ammonia borine 4.31 grams.Revolve steaming for twice and always collect to such an extent that ammonia borine crystal 12.56 restrains, yield is 81%.Its purity of X-ray powder diffraction analysis to product is 97%, and test result is as shown in Figure 2.
Embodiment 2:
In the argon gas glove box, take by weighing the NaBH that ball-milling processing is in advance crossed
41.9 gram, (NH
4)
2CO
32.5 gram (ball milling condition is 200rpm, and the sample particle yardstick is in hundred nanometers), and measure 30 milliliters of THF.With three pack in the lump (100 milliliters of volumes) in the commercial autoclave.Magnetic stirring apparatus is inserted in the airtight back of tank body to be stirred; Control temperature of reaction kettle simultaneously at 50 ℃; Reaction is carried out after 5 hours autoclave being connected with tensimeter; Measure a jar internal pressure 60psi, calculating gained hydrogen amount by equation for ideal gases is 0.0108mol, and the confirmation reaction is carried out degree and is merely 21.6%.This shows, even if the sample that conventional stirring reaction is crossed for ball-milling processing also is difficult to accomplish preparation feedback.Though the rising temperature of reaction can further promote speed of response, the risk of also bringing ammonia borine product to decompose.Equally above-mentioned weighing sample and THF are placed small-sized ball grinder (180 milliliters) for 30 milliliters, 100rpm and 45 ℃ of following ball-milling processing only 15 minutes, a jar internal pressure promptly reached preset value 128psi, shows the reaction termination.Above-mentioned comparing result discloses the high efficiency of temperature control ball milling method on ammonia borine building-up reactions undoubtedly.
Embodiment 3:
In the argon gas glove box, take by weighing 19 gram NaBH4,33.5 gram (NH
4)
2SO
4(there have slightly to be excessive, to avoid NaBH
4Residue also is dissolved in THF), and measure 500 milliliters of THF.With three pack in the lump voluntarily (2 liters of volumes) in the ball grinder of processing.Tank body is packed into after airtight planetary ball mill (Fischt PM-400) is accurately controlled the ball milling chambers temp in 45 ℃, and ball milling is 60 minutes under 100rpm.Ball grinder is connected with tensimeter, measures a jar internal pressure 128psi, calculating gained hydrogen amount by equation for ideal gases is 0.5mol, confirms to react fully and accomplishes.Hydrogen in the jar is discharged, shift out white slurry to 600 milliliter tophan pot.Centrifugal treating 15min under the 3000r/min rotating speed, gained clear liquid partly move in 1 liter of round-bottomed bottle, place the Rotary Evaporators underpressure distillation.Promptly get the crystallization of white ammonia borine after THF removes, take out and be weighed as 8.5 grams.Revolve and steam the THF collect and pour into once more in the centrifugal gained solid residue.Room-temperature ball-milling was handled 15 minutes under the 100rpm, and repeated centrifugation is revolved the steaming treating processes, and reextraction obtains ammonia borine 4.52 grams.Revolve steaming for twice and always collect to such an extent that ammonia borine crystal 13.02 restrains, yield is 84%.Its purity of X-ray powder diffraction analysis to product is 94%.
Embodiment 4:
In the argon gas glove box, take by weighing 27.9 gram KBH
4, 24.8 the gram (NH
4)
2CO
3(there have slightly to be excessive, to avoid KBH
4Residue also is dissolved in THF), and measure 500 milliliters of THF.With three pack in the lump voluntarily (2 liters of volumes) in the ball grinder of processing.Tank body is packed into after airtight planetary ball mill (Fischt PM-400) is accurately controlled the ball milling chambers temp in 45 ℃, and ball milling is 45 minutes under 100rpm.Ball grinder is connected with tensimeter, measures a jar internal pressure 128psi, calculating gained hydrogen amount by equation for ideal gases is 0.5mol, confirms to react fully and accomplishes.Hydrogen in the jar is discharged, shift out white slurry to 600 milliliter tophan pot.Centrifugal treating 15min under the 3000rpm rotating speed, gained clear liquid partly move in 1 liter of round-bottomed bottle, place the Rotary Evaporators underpressure distillation.Promptly get the crystallization of white ammonia borine after THF removes, take out and be weighed as 8.1 grams.Revolve and steam the THF collect and pour into once more in the centrifugal gained solid residue.Room-temperature ball-milling was handled 15 minutes under the 100rpm, and repeated centrifugation is revolved the steaming treating processes, and reextraction obtains ammonia borine 4.3 grams.Revolve steaming for twice and always collect to such an extent that ammonia borine crystal 12.4 restrains, yield is 80%.Its purity of X-ray powder diffraction analysis to product is 96%.
Claims (9)
1. wet-chemical prepares the method for ammonia borine; It is characterized in that: with ammonium salt, hydroborate is raw material, is reaction medium with the organic solvent, adopts the temperature control ball milling method to carry out building-up reactions; Slurry behind the ball-milling reaction goes out clear liquid through spinning, after revolve and steam clear liquid and obtain purity and reach 97% ammonia borine; The centrifugal solids that obtains is carried out the secondary solvent extraction, can make yield reach 81%;
The mole proportioning of described raw material is: ammonium salt: hydroborate: organic solvent=1:0.3～3:5～12; The ball-milling processing TR is 0～100 ° of C.
2. preparation method as claimed in claim 1 is characterized in that: described secondary solvent extraction is the way that adopts the temperature control ball milling, places ball grinder to carry out secondary temperature control ball-milling processing with revolving the organic solvent that steams collection separating obtained solid; The ball-milling processing TR is 0～100 ° of C.
3. preparation method as claimed in claim 1 is characterized in that: the pellet mass ratio of described ball milling is: 0.1～30.
4. preparation method as claimed in claim 1 is characterized in that: the speed range of described ball milling is: 10～600rpm.
5. preparation method as claimed in claim 1 is characterized in that: described initial reactant carries out building-up reactions in ball grinder;
Described ball grinder is airtight ball grinder, and the vapor pipe of being with valve is equipped with in covering of ball grinder, can be connected with tensimeter, so that monitor a jar internal pressure in real time.
6. preparation method as claimed in claim 5 is characterized in that: the volume scope of described ball grinder is: 50～5000ml.
7. preparation method as claimed in claim 5 is characterized in that: described ball grinder is the ball grinder that planetary or horizontal ball milling chamber can be heated.
8. preparation method as claimed in claim 5; It is characterized in that: the said ball milling time is confirmed through monitoring ball grinder internal pressure; Promptly calculate the amount of by product hydrogen after the complete reaction through material quantity; And then sealing the theoretical pressure in the ball grinder after calculating complete reaction, whether complete constantly monitoring ball grinder internal pressure is definite in the mechanical milling process reacts.
9. preparation method as claimed in claim 1 is characterized in that: said organic solvent is the organic medium tetrahydrofuran THF or the ether of solubilized hydroborate; Ammonium salt is volatile salt, ammonium chloride or ammonium sulfate; Hydroborate is lithium borohydride or Peng Qinghuana.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105189072A (en) * | 2013-03-27 | 2015-12-23 | 株式会社神户制钢所 | Kneader and kneading method |
| CN105984848A (en) * | 2015-02-13 | 2016-10-05 | 上海福乐医药科技有限公司 | Preparation method for ammonia borane |
| CN108623493A (en) * | 2018-06-20 | 2018-10-09 | 大连理工大学 | With CO under a kind of temperate condition2For the N- formylated synthetic methods of carbon source |
| CN111620302A (en) * | 2020-06-11 | 2020-09-04 | 有研工程技术研究院有限公司 | Metal amino borane composite hydrogen storage material |
| CN113716581A (en) * | 2021-09-13 | 2021-11-30 | 中国人民解放军国防科技大学 | High-ceramic-yield carbon-free boron nitride precursor and synthesis method thereof |
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| WO2009072989A2 (en) * | 2007-12-05 | 2009-06-11 | National University Of Singapore | A hydrogen storage material and a process for release of hydrogen |
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2010
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| WO2009072989A2 (en) * | 2007-12-05 | 2009-06-11 | National University Of Singapore | A hydrogen storage material and a process for release of hydrogen |
| CN101613083A (en) * | 2008-06-27 | 2009-12-30 | 中国科学院金属研究所 | Metal ammonia borane compound hydrogen storage material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105189072A (en) * | 2013-03-27 | 2015-12-23 | 株式会社神户制钢所 | Kneader and kneading method |
| CN105189072B (en) * | 2013-03-27 | 2017-07-28 | 株式会社神户制钢所 | Mixing and blending machine and mixing method |
| US10265884B2 (en) | 2013-03-27 | 2019-04-23 | Kobe Steel, Ltd. | Kneader and kneading method |
| CN105984848A (en) * | 2015-02-13 | 2016-10-05 | 上海福乐医药科技有限公司 | Preparation method for ammonia borane |
| CN108623493A (en) * | 2018-06-20 | 2018-10-09 | 大连理工大学 | With CO under a kind of temperate condition2For the N- formylated synthetic methods of carbon source |
| CN108623493B (en) * | 2018-06-20 | 2021-01-19 | 大连理工大学 | Under mild condition with CO2N-formylation synthesis method for carbon source |
| CN111620302A (en) * | 2020-06-11 | 2020-09-04 | 有研工程技术研究院有限公司 | Metal amino borane composite hydrogen storage material |
| CN113716581A (en) * | 2021-09-13 | 2021-11-30 | 中国人民解放军国防科技大学 | High-ceramic-yield carbon-free boron nitride precursor and synthesis method thereof |
| CN113716581B (en) * | 2021-09-13 | 2023-03-14 | 中国人民解放军国防科技大学 | High-ceramic-yield carbon-free boron nitride precursor and synthesis method thereof |
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Application publication date: 20120704 |