CN101654223A - Method for preparing sodium borohydride by recycling sodium metaborate - Google Patents
Method for preparing sodium borohydride by recycling sodium metaborate Download PDFInfo
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- CN101654223A CN101654223A CN200810012860A CN200810012860A CN101654223A CN 101654223 A CN101654223 A CN 101654223A CN 200810012860 A CN200810012860 A CN 200810012860A CN 200810012860 A CN200810012860 A CN 200810012860A CN 101654223 A CN101654223 A CN 101654223A
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- Prior art keywords
- sodium borohydride
- sodium
- metaborate
- hydrogen
- sodium metaborate
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- 229910000033 sodium borohydride Inorganic materials 0.000 title claims abstract description 45
- 239000012279 sodium borohydride Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 37
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000004064 recycling Methods 0.000 title abstract 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000001257 hydrogen Substances 0.000 claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 34
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910012375 magnesium hydride Inorganic materials 0.000 claims abstract description 21
- 229910052786 argon Inorganic materials 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 238000003801 milling Methods 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 abstract description 4
- 230000002829 reductive effect Effects 0.000 abstract description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052796 boron Inorganic materials 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- 238000012856 packing Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000994 depressogenic effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002680 magnesium Chemical class 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The invention relates to a method for preparing alkali metals hydroboron, in particular to a method for preparing sodium borohydride by recycling sodium metaborate, which solves the problem of recycling a byproduct sodium metaborate after the sodium borohydride is hydrolyzed to prepare hydrogen in the prior art, and is a novel method for preparing the sodium borohydride. The method takes magnesiumhydride as a hydrogen source and the sodium metaborate as a boron source, and prepares the sodium borohydride through mechanical and chemical reaction. In the presence of the hydrogen, magnesium powder is hydrogenated at certain temperature and pressure to prepare magnesium hydride; and the sodium metaborate and the magnesium hydride in a certain ratio are put into a ball mill, certain argon or hydrogen pressure, ratio of grinding media to material and grinding time are maintained, and the sodium metaborate can be reduced into the sodium borohydride. The method has the advantages of simple, convenient and safe process, no environmental pollution and the like.
Description
Technical field
The present invention relates to the preparation method of hydroborate, a kind of specifically recycle sodium metaborate prepares the method for sodium borohydride.
Background technology
Sodium borohydride is good reductive agent and hydrogen storage material, particularly as a kind of hydrogen storage material, can hydrolytic hydrogen production, and become the hydrogen source carrier of fuel cell.There has been the broad variety sodium borohydride fuel cell to occur at present.After this fuel cell used, its by product was a sodium metaborate.This material cycle utilization is prepared sodium borohydride, will avoid causing the waste of environmental pollution and resource.Therefore be a very significant job.
At present, prepare NaBH by sodium metaborate
4Method mainly comprise electrolytic process and high temperature and high pressure method.Electrolytic process is to be that the direct electrolysis of raw material forms sodium borohydride with the sodium metaborate.The bottleneck problem that this technology runs into is the OH that exists in the electrolytic process
-Preferentially on electrode, separate out, make BO
2 -The efficient of separating out into boron hydrogen radical ion is extremely low, thereby can't realize suitability for industrialized production.And high temperature and high pressure method is similar to the process that traditional bayer's process prepares sodium borohydride, and whole process adopts high temperature, high pressure, and reaction conditions and operation control are all very strict.Because temperature of reaction is near the decomposition temperature of sodium borohydride, and reaction conditions under high pressure carries out, therefore the control reaction is difficult, occurs explosion hazard easily.
As shown in Figure 3, Bayer Bayer method (US Pat, 1969.3471268; US Pat, 1963.3077376 and US Pat, 1965,3164441) typical process flow is as follows: borax and reductive agent place the stainless steel autoclave, and logical hydrogen is under 4-7MPa, 100-600 ℃, Mg/Al/Na, reacted 2-4 hour, and be cooled to room temperature, take out product.
Reaction formula is as follows: Na
2B
4O
7+ 16Na+8H
2+ 7SiO
2-4NaBH
4+ 7Na
2SiO
3
Bayer Bayer method is to equipment requirements very high (higher temperature and pressure), operational condition harshness.
Summary of the invention
In order to realize the recycle of sodium metaborate, the invention provides the method that a kind of recycle sodium metaborate prepares sodium borohydride, use high energy ball mill to grind the preparation sodium borohydride, put the problem that by product utilizes again behind the hydrogen to solve the sodium borohydride fuel cell hydrolysis.
Technical scheme of the present invention is:
The present invention is a raw material with sodium borohydride hydrolysate sodium metaborate, with the by product sodium metaborate of chemical machinery mechanics method after with preparing hydrogen by sodium borohydride hydrolysis, prepares sodium borohydride with the magnesium hydride mixing and ball milling, and the recycle sodium metaborate prepares sodium borohydride.
A kind of recycle sodium metaborate prepares the method for sodium borohydride, and with the method for chemical machinery mechanics method, adopting magnesium powder, sodium metaborate is raw material, concrete steps are as follows: at first, the magnesium powder is carried out hydrogenation under 100-300 ℃ and hydrogen pressure 1-7MPa, make magnesium hydride, reaction formula: Mg+H
2-MgH
2Then, four water sodium metaborates do not have water treatment, with anhydrous sodium metaborate x, magnesium hydride y, according to mol ratio x: y=1: (2-4) put into ball-grinding machine, feed argon gas or hydrogen, keep argon gas or hydrogen 100-500kPa, ball material mass ratio (10: 1)-(100: 1) and milling time 0.5-4h, can obtain sodium borohydride, reaction formula: NaBO
2+ 2MgH
2-NaBH
4+ 2MgO.
The present invention makes extraction agent with Isopropylamine, and reaction product Isopropylamine stirring and dissolving after filtration, underpressure distillation, reclaims solvent, obtains white solid state product sodium borohydride.
The invention has the beneficial effects as follows:
1, the present invention is a hydrogen source with the magnesium hydride, is the boron source with the sodium metaborate, by the mechanical mill preparation sodium borohydride that combines with chemical reaction.In inert atmosphere, the magnesium powder under certain temperature and pressure, is carried out hydrogenation, make magnesium hydride; Then anhydrous sodium metaborate, magnesium hydride are put into ball mill according to certain ratio, keep certain pressure, ratio of grinding media to material and milling time, can obtain sodium borohydride, the sodium borohydride purity of this method preparation reaches more than 90% productive rate about 70%.Adopt preparing sodium borohydride by chemical mechanical mechanics method, not only can the recycle sodium metaborate, compare with the preparation technology of present sodium borohydride, have that raw materials cost is low, a technology handy and safe, advantage such as pollution-free.
2, the recycle that realizes sodium metaborate with chemical machinery mechanics method provided by the invention.Reaction conditions is to carry out under room temperature, the low pressure inert atmosphere.Reaction is control easily, and process is safe and reliable.Adopting magnesium hydride in the experiment is hydrogen source, has reduced the cost of preparation sodium borohydride, and whole process is pollution-free, and process stabilizing is easy to realize, adopts this method to prepare sodium borohydride, has not yet to see the domestic and foreign literature report.
Description of drawings
Fig. 1: the XRD phasor of sodium borohydride of the present invention and standard relatively.
Fig. 2: sodium borohydride scanning electron microscope photograph of the present invention (sodium borohydride appearance).
Fig. 3: the typical process flow synoptic diagram of high temperature and high pressure method.
Embodiment
Embodiment 1:
1. starting material are handled
Handle four water sodium metaborates with vacuum drying oven, 120～220 ℃, more than the dry 4h, eliminate crystal water, it is standby to make anhydrous sodium metaborate.
2. synthesizing hydrogenated magnesium
Take by weighing 60g magnesium powder (crossing 200 mesh sieves) and add autoclave (GCF-1 autoclave), the envelope still, applying argon gas vacuumizes, and 3 times repeatedly, connect power supply again autoclave is heated to 300 ℃, fill hydrogen then to 6.0MPa, reaction 24h.Stop heating after reaction finishes, be cooled to room temperature, unload and be depressed into normal pressure, applying argon gas protection product.
3. synthetic sodium borohydride
Take by weighing the anhydrous sodium metaborate of 1.32g, 1.4g magnesium hydride; the ball grinder (QM-3A vibration at high speed ball mill) of packing into; by certain charging than (ball material mass ratio 10: the 1) steel ball of packing into; vacuumize then; applying argon gas, three times repeatedly, last applying argon gas (200kPa) protection; ball milling 2h opens a jar taking-up product after the cooling.With Isopropylamine stirring and dissolving 1h, after filtration, underpressure distillation, reclaim solvent, obtain white solid state product sodium borohydride.
Productive rate is 70%, and purity is greater than 90% (calculating with active hydrogen).
Embodiment 2:
1. starting material are handled
Handle four water sodium metaborates with vacuum drying oven, 120～220 ℃, more than the dry 4h, eliminate crystal water, it is standby to make anhydrous sodium metaborate.
2. synthesizing hydrogenated magnesium
Take by weighing 60g magnesium powder (crossing 200 orders) and add autoclave (GCF-1 autoclave), the envelope still, applying argon gas vacuumizes, and 3 times repeatedly, connect power supply again autoclave is heated to 200 ℃, fill hydrogen then to 4.5MPa, reaction 24h.Stop heating after reaction finishes, be cooled to room temperature, unload and be depressed into normal pressure, applying argon gas protection product.
3. synthetic sodium borohydride
Take by weighing the anhydrous sodium metaborate of 1.32g, 1.4g magnesium hydride; the ball grinder (QM-3A vibration at high speed ball mill) of packing into; by certain charging than (ball material mass ratio 30: the 1) steel ball of packing into; vacuumize then; applying argon gas, three times repeatedly, last applying argon gas (200kPa) protection; ball milling 2h opens a jar taking-up product after the cooling.With Isopropylamine stirring and dissolving 1h, after filtration, underpressure distillation, reclaim solvent, obtain white solid state product sodium borohydride.Productive rate is 65%, and purity is greater than 90% (calculating with active hydrogen).
Embodiment 3:
1. starting material are handled
Handle four water sodium metaborates with vacuum drying oven, 120～220 ℃, more than the dry 4h, eliminate crystal water, it is standby to make anhydrous sodium metaborate.
2. synthesizing hydrogenated magnesium
Take by weighing 60g magnesium powder (crossing 200 orders) and add autoclave (GCF-1 autoclave), the envelope still, applying argon gas vacuumizes, and 3 times repeatedly, connect power supply again autoclave is heated to 300 ℃, fill hydrogen then to 6.0MPa, reaction 24h.Stop heating after reaction finishes, be cooled to room temperature, unload and be depressed into normal pressure, applying argon gas protection product.
3. synthetic sodium borohydride
Take by weighing the anhydrous sodium metaborate of 1.32g, 1.0g magnesium hydride; the ball grinder (QM-3A vibration at high speed ball mill) of packing into; by certain charging than (ball material mass ratio 50: the 1) steel ball of packing into; vacuumize then; applying argon gas, three times repeatedly, last applying argon gas (200kPa) protection; ball milling 2h opens a jar taking-up product after the cooling.With Isopropylamine stirring and dissolving 1h, after filtration, underpressure distillation, reclaim solvent, obtain white solid state product sodium borohydride.
Productive rate is 60%, and purity is greater than 90% (calculating with active hydrogen).
Qualification result is as follows:
1. ultimate analysis (wt%)
B(％)27.72 H(％)10.39
B∶H(mol)＝1∶4.02
2. XRD figure picture, consistent with standard picture (D8 DISCOVER x-ray diffractometer, German Brooker AXS company) as shown in Figure 1.
3. as shown in Figure 2, photomicrography (KYKY-EM3200), from photograph as can be seen crystal be the complete cubes of rule.
Embodiment 4
Difference from Example 1 is:
The magnesium powder is carried out mechanical mill and hydrogen reacts under 300 ℃ and hydrogen pressure 6MPa, make magnesium hydride; With anhydrous sodium metaborate 1.6g, magnesium hydride 1.0g, put into ball-grinding machine, keep argon pressure 200kPa, ball material mass ratio 50: 1 and milling time 0.5h.
Productive rate is 55%, and purity is greater than 90% (calculating with active hydrogen).
Embodiment 5
Difference from Example 1 is:
The magnesium powder is carried out mechanical mill and hydrogen reacts under 300 ℃ and hydrogen pressure 5MPa, make magnesium hydride; With anhydrous sodium metaborate 2.2g, magnesium hydride 2.3g, put into ball-grinding machine, keep argon pressure 200kPa, ball material mass ratio 30: 1 and milling time 2h.
Productive rate is 71%, and purity is greater than 90% (calculating with active hydrogen).
Embodiment 6
Difference from Example 1 is:
The magnesium powder is carried out mechanical mill and hydrogen reacts under 300 ℃ and hydrogen pressure 6MPa, make magnesium hydride; With sodium metaborate 1.32g, magnesium hydride 1.4g, put into ball-grinding machine, keep argon pressure 200kPa, ball material mass ratio 50: 1 and milling time 4h.
Productive rate is 60%, and purity is greater than 90% (calculating with active hydrogen).
Claims (2)
1. a recycle sodium metaborate prepares the method for sodium borohydride, it is characterized in that, adopting magnesium powder, anhydrous sodium metaborate is raw material, concrete steps are as follows: at first, the magnesium powder is carried out hydrogenation under 100-300 ℃ and hydrogen pressure 1-7MPa, make magnesium hydride, reaction formula: Mg+H
2-MgH
2Then, four water sodium metaborates are removed water treatment, be prepared into anhydrous sodium metaborate; With anhydrous sodium metaborate x, magnesium hydride z, according to mol ratio x: y=1: 2-5 puts into ball-grinding machine, feeds argon gas or hydrogen, keeps argon gas or hydrogen pressure 100-500kPa, ball material mass ratio 10: 1-100: 1 and milling time 0.5-4h, can obtain sodium borohydride, reaction formula: NaBO
2+ 2MgH
2-NaBH
4+ 2MgO.
2. prepare the method for sodium borohydride according to the described recycle sodium metaborate of claim 1, it is characterized in that: sodium borohydride is made extraction agent with Isopropylamine, reaction product Isopropylamine stirring and dissolving, filter, solvent is reclaimed in underpressure distillation, obtains white solid state product sodium borohydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810012860A CN101654223A (en) | 2008-08-20 | 2008-08-20 | Method for preparing sodium borohydride by recycling sodium metaborate |
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|---|---|---|---|
| CN200810012860A CN101654223A (en) | 2008-08-20 | 2008-08-20 | Method for preparing sodium borohydride by recycling sodium metaborate |
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| Publication Number | Publication Date |
|---|---|
| CN101654223A true CN101654223A (en) | 2010-02-24 |
Family
ID=41708719
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|---|---|---|---|
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|---|---|---|---|---|
| EP2623457A1 (en) | 2012-02-02 | 2013-08-07 | VTU Holding GmbH | Use of an ionic liquid for storing hydrogen |
| CN105018957A (en) * | 2015-08-13 | 2015-11-04 | 黎吉星 | Hydrogen powder manufacturing method |
| CN105271119A (en) * | 2015-05-18 | 2016-01-27 | 深圳市国创新能源研究院 | Method for preparing sodium borohydride |
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| CN114436209A (en) * | 2022-03-08 | 2022-05-06 | 广东省科学院资源利用与稀土开发研究所 | Magnesium hydride-in-situ generated metal borohydride hydrolysis hydrogen production material and preparation method thereof |
| CN114436209B (en) * | 2022-03-08 | 2023-07-14 | 广东省科学院资源利用与稀土开发研究所 | Magnesium hydride-in-situ generated metal borohydride hydrolysis hydrogen production material and preparation method thereof |
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