CN101575101A - Large-scale preparation method for amino borane - Google Patents
Large-scale preparation method for amino borane Download PDFInfo
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- CN101575101A CN101575101A CNA2008100112938A CN200810011293A CN101575101A CN 101575101 A CN101575101 A CN 101575101A CN A2008100112938 A CNA2008100112938 A CN A2008100112938A CN 200810011293 A CN200810011293 A CN 200810011293A CN 101575101 A CN101575101 A CN 101575101A
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- amino borane
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- scale preparation
- amino
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- TVJORGWKNPGCDW-UHFFFAOYSA-N aminoboron Chemical compound N[B] TVJORGWKNPGCDW-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 10
- 238000001291 vacuum drying Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 229910000085 borane Inorganic materials 0.000 claims description 12
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 12
- 238000011085 pressure filtration Methods 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 9
- 238000007738 vacuum evaporation Methods 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012448 Lithium borohydride Substances 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 23
- 239000002904 solvent Substances 0.000 abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 10
- 239000001257 hydrogen Substances 0.000 abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 10
- 238000005406 washing Methods 0.000 abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract description 5
- 230000006837 decompression Effects 0.000 abstract description 4
- 238000001704 evaporation Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 abstract 1
- 239000001099 ammonium carbonate Substances 0.000 abstract 1
- 235000012501 ammonium carbonate Nutrition 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000006210 lotion Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 235000017550 sodium carbonate Nutrition 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000012797 qualification Methods 0.000 description 3
- 229910010082 LiAlH Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005649 metathesis reaction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000003380 propellant Substances 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 241000720974 Protium Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002498 deadly effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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Abstract
The invention relates to an amino borane preparation technology, in particular to a large-scale preparation method for amino borane. The method comprises the following steps: directly synthesizing amino borane by reaction raw materials including hydroborate and ammonia source in organic solvent, wherein the hydroborate, the ammonia source and the organic solvent are added into a reaction vessel for reaction at a mol ratio of 1:1-3:1.5-3; compressing, filtering, vacuum-evaporating and vacuum-drying the product of reaction to obtain the amino borane with the weight and the purity above 90 percent and the yield rate above 80 percent. After being purified and added into the reaction vessel, the organic solvent is blended and stirred with sodium borohydride and ammonium carbonate which are added into the reaction vessel in advance, and the hydrogen is released and collected; reaction pulp is conveyed into a filter and compressed and filtered under the protection of nitrogen, and after the filter residue is fully washed with solvent, sodium carbonate is collected; and the washing liquor and the filter liquor are blended and conveyed into a decompression evaporation tower, and finally the amino borane is obtained. Therefore, the method has the advantages of moderate reaction conditions, easy control, simple required devices and large-scale production as required.
Description
Technical field
The present invention relates to the amino borane technology of preparing, be specially a kind of large-scale preparation method for amino borane.
Background technology
The research of amino borane starts from the fifties, mainly is applied in the research of induced with laser nuclear fusion reaction.Because do not have suitable Application Areas, its research stays cool.In recent years; because energy shortage and environment protection need in the world wide; energy structure is changed to Hydrogen Energy trend by non-renewable fossil energy; the amino borane hydrogen richness is higher; carrying material as Hydrogen Energy, is that the focus compound of hydrogen storage material area research in recent years [is seen document: Z.T.Xiong, C.K.Yong; G.T.Wu; P.Chen, W.Shaw, A.Karkamkar; T.Autrey; M.O.Jones, S.R.Johnson, P.P.Edwards; W.I.F.David, Nature Mater.7 (2008): 138-141].Simultaneously, owing to contain higher protium and boron in the amino borane, energy density is up to-33.8kJ/g, as rocket propellant, than the liquid hydrazine energy density-32.2kJ/g height of present use; Though its weight density is lower than liquid hydrogen-120.9kJ/g, its volume density-25.0kJ/cm3 has superiority than liquid hydrogen-8.5kJ/cm3.Amino borane normal temperature is down solid-state simultaneously, and stable in properties is more convenient than liquid hydrazine and liquid hydrogen in the use, so amino borane, has certain prospect as a kind of solid rocket propellant or additive.In addition, because its burning thermal discharge height of amino borane, and room temperatures properties is stable, and the combustible agent that contains the fiery explosive of energy as height also has better prospect.Therefore, the scale preparation technology of researching and developing this high energy-containing compound has great significance.At present, the amino borane preparation mainly contains two kinds of methods, is divided into borine method and sodium borohydride method according to its boron source.(the Shore method is seen document: S.G.Shore, K.W. to the borine method
Inorg.Chem.3 (1963): 914-915), be the boron source with borine ,-78 ℃ and liquefied ammonia reaction directly generate amino borane.Because borine is a kind of inflammable, deadly poisonous compound, produces very dangerous.The U.S. once developed the suitability for industrialized production of borine in the 50-60 age, all stop.In addition, the borine preparation consumes a large amount of LiAlH in the Shore method
4Therefore, whole technology cost height, equipment are comparatively complicated.The sodium borohydride method of bibliographical information also claims improved borine method [seeing document: S.G.Shore, Chen X.N., Patent:WO2007/120511], replaces LiAlH with sodium borohydride
4, generate borine with the iodine reaction, borine is caught with organic compound, again with ammonia gas react, prepare the method for amino borane.Use borine equally in this method reaction process, if in actual amplification process, occur leaking etc., consequence is serious; Therefore, shore method and improved shore method all are not suitable for suitability for industrialized production.
Summary of the invention
The object of the present invention is to provide a kind of large-scale preparation method for amino borane, its reaction conditions gentleness, control easily, scale is amplified production according to actual needs.
Technical scheme of the present invention is:
A kind of large-scale preparation method for amino borane, adopt reaction raw materials hydroborate, ammonia source direct synthesizing amino borine in organic solvent, with hydroborate, ammonia source, organic solvent in molar ratio 1: (1~3): the proportioning of (1.5~3) once joins in the reactor reacts; Product is through pressure filtration, vacuum-evaporation, vacuum-drying, obtains weight purity more than 90%, the amino borane of yield more than 80%.
Described hydroborate is sodium borohydride, POTASSIUM BOROHYDRIDE or lithium borohydride.
Described ammonia source is a volatile salt, perhaps is ammonia and CO
2Gas mixture, ammonia and CO
2Volume ratio be 2: (0.5~1.5); Described organic solvent is tetrahydrofuran (THF), ether, hexanaphthene or normal hexane.
Described large-scale preparation method for amino borane, 0~100 ℃ of temperature of reaction, preferred 20~50 ℃.
The pressure range of described pressure filtration operation is 1~2.5atm.
The vacuum tightness of described vacuum-evaporation operation is 0~0.098MPa, and temperature is-5~100 ℃.
The preferred vacuum tightness of described vacuum-evaporation operation is 0.07~0.098MPa, and preferred temperature is 0~50 ℃.
Described vacuum-drying service temperature is 0~100 ℃, is preferably 20~50 ℃.
The invention has the beneficial effects as follows:
1, present, the research of adopting hydroborate, ammonia source direct reaction to prepare amino borane does not have the technology and the technology of large-scale production.Therefore, it is main raw material that the present invention adopts hydroborate, volatile salt or ammonia, carbon dioxide mix gas, and raw material and organic solvent once join in the reactor, and through replacement(metathesis)reaction, decomposition reaction, the direct production amino borane at home and abroad still belongs to the first time.
2, the utility model required equipment is simple, and the technology of medium-scaleization production is provided, and scale is amplified production according to actual needs.Sodium borohydride is reacted with volatile salt, directly generate amino borane, its reaction conditions gentleness, control easily, by product is hydrogen and yellow soda ash, can be used as the by-product utilization of this technology.Whole process hazard is little, can not pollute environment, is the chemical process of a Sustainable development.
3, the present invention adopt with organic solvent purified after, be added in the reactor, mixes with the sodium borohydride that adds reactor in advance, volatile salt or ammonia, carbon dioxide mix gas, stir, discharge the hydrogen collection.Reaction slurry is sent into filter, pressure filtration under nitrogen or protection of inert gas, filter residue is collected as yellow soda ash after using the solvent thorough washing.Washing lotion with send into the reduction vaporization tower filtrate mixing, adopt the present invention to obtain amino borane, product is a white solid, after filtration, operations such as washing, drying, purifying, weight purity can reach 90%, yield can reach 80%.
4, cost of the present invention is lower.
Description of drawings
Fig. 1 is an amino borane synthesis process flow diagram of the present invention.
Among the figure, 1 solvent storage tank; 2 solvent purified reaction towers; 3 reactors; 4 pressure filters; 5 decompression evaporators.
Fig. 2 is the amino borane X-ray diffractogram.
Embodiment
Employing hydroborate that the present invention proposes and volatile salt (or ammonia, CO
2Gas mixture) direct reaction is realized the amino borane large-scale production, and main processes comprises (see figure 1): processes such as metathesis under organic solvent purifying, batching, the inert atmosphere, decomposition reaction, pressure filtration, washing, vacuum-evaporation, the packing of product.
As shown in Figure 1, present device is made of solvent storage tank 1, solvent purified reaction tower 2, reactor 3, pressure filter 4, decompression evaporator 5 etc., solvent storage tank 1 passes through pipeline connection with solvent purified reaction tower 2, be connected with venting port on the solvent purified reaction tower 2, reactor 3 is communicated with solvent purified reaction tower 2 and pressure filter 4 by pipeline respectively, and decompression evaporator 5 is communicated with pressure filter 4 and solvent storage tank 1 by pipeline respectively.
Organic solvent in the solvent storage tank 1 is added in the reactor 3 behind solvent purified reaction tower 2 purifying, mixes with the sodium borohydride that adds reactor in advance, volatile salt, stir constantly reaction, be reflected in 20 ℃~50 ℃ recirculated waters and carry out, the hydrogen that discharges is collected, and carries out recover hydrogen.After reaction for some time, no gas is emerged in the reactor 3, and react and be precipitated as yellow soda ash in the mixed liquor this moment, and amino borane is dissolved in the organic solvent.To react mixed liquor and send into pressure filter 4, pressure filtration under 0.5~2.5atm nitrogen or protection of inert gas, filter residue is collected after with the solvent thorough washing, and filter residue yellow soda ash is byproduct; Washing lotion with send into reduction vaporization tower 5 filtrate mixing.The certain vacuum degree (under the vacuum tightness 0.07~0.098MPa), vacuum evaporating solvent, the acquisition product is a white solid, carries out finished product detection, packing, organic solvent is recycled to solvent storage tank 1 and utilizes.Products obtained therefrom can obtain the finished product of weight purity 90% after vacuum-drying.Adopt hydroborate method macro preparation amino borane, chemical equation is as follows:
The present invention is described in more detail below by embodiment.
With sodium borohydride 151.2g, volatile salt 384g, join successively in proportion in the reactor through anhydrous tetrahydro furan (THF) 12mol of processed, whole process all under the nitrogen gas stream protection (nitrogen pressure is 1.5atm) carry out.45 ℃ of reaction employing water-bath temperature controls stir, and wait to stop to generate gas, and reaction finishes, and the pressure filtration moulding pressure is 1.5atm, and filter residue washs 3 times with 2L anhydrous tetrahydro furan (THF), and washing lotion is mixed with filtrate, vacuum-evaporation, 30 ℃ of temperature, vacuum tightness 0.098MPa.Solvent recuperation, solid is weighed after 30 ℃ of vacuum-drying, and yield is 80%, and reaction product is a white solid, weight purity 90%, qualification result is as follows:
1. ultimate analysis: B, 30.2%wt; H, 18.9%; N, 44.9%; C, 6.0%wt;
2.X the ray material phase analysis is seen Fig. 2, as seen from Figure 2: the product that the present invention obtains is corresponding fully with amino borane standard spectrum peak, does not have impurity peaks to occur.
Embodiment 2
POTASSIUM BOROHYDRIDE 151.2g, volatile salt 1152g, hexanaphthene 18mol are joined in the reactor in proportion successively, whole process all under nitrogen gas stream protection (nitrogen pressure is 2atm) carry out.40 ℃ of reaction employing water-bath temperature controls stir, and wait to stop to generate gas, and reaction finishes, and the pressure filtration moulding pressure is 2atm, and filter residue washs 3 times with the 2L hexanaphthene, and washing lotion is mixed with filtrate, vacuum-evaporation, 40 ℃ of temperature, vacuum tightness 0.07MPa.Solvent recuperation, solid is weighed after 40 ℃ of vacuum-drying, and yield is 82%, and reaction product is a white solid, weight purity 93%, qualification result is as follows:
Ultimate analysis: B, 31%wt; H, 19.3%wt; N, 45.4%wt; C, 4.3%wt.
With lithium borohydride 151.2g, ammonia and CO
2Gas mixture (ammonia 8mol, ammonia and CO
2Volume ratio be 2: 1), normal hexane 6mol joins in the reactor in proportion successively, whole process all under the nitrogen gas stream protection (nitrogen pressure is 1.8atm) carry out.50 ℃ of reaction employing water-bath temperature controls stir, and wait to stop to generate gas, and reaction finishes, and the pressure filtration moulding pressure is 1.8atm, and filter residue washs 3 times with the 2L normal hexane, and washing lotion is mixed with filtrate, vacuum-evaporation, 50 ℃ of temperature, vacuum tightness 0.08MPa.Solvent recuperation, solid is weighed after 50 ℃ of vacuum-drying, and yield is 85%, and reaction product is a white solid, weight purity 95%, qualification result is as follows:
Ultimate analysis: B, 31.6%wt; H, 19.4%wt; N, 45.8%wt; C, 3.2%wt.
Claims (8)
1. large-scale preparation method for amino borane, it is characterized in that, adopt reaction raw materials hydroborate, ammonia source direct synthesizing amino borine in organic solvent, the proportioning of hydroborate, ammonia source, organic solvent 1: 1 in molar ratio~3: 1.5~3 is once joined in the reactor react; Product is through pressure filtration, vacuum-evaporation, vacuum-drying, obtains weight purity more than 90%, the amino borane of yield more than 80%.
2. press claims 1 described large-scale preparation method for amino borane, it is characterized in that, described hydroborate is sodium borohydride, POTASSIUM BOROHYDRIDE or lithium borohydride.
3. press claims 1 described large-scale preparation method for amino borane, it is characterized in that, described ammonia source is a volatile salt, perhaps is ammonia and CO
2Gas mixture, ammonia and CO
2Volume ratio be 2: 0.5~.5.
4. press claims 1 described large-scale preparation method for amino borane, it is characterized in that, described organic solvent is tetrahydrofuran (THF), ether, hexanaphthene or normal hexane.
5. press claims 1 described large-scale preparation method for amino borane, it is characterized in that, 0~100 ℃ of temperature of reaction.
6. press claims 1 described large-scale preparation method for amino borane, it is characterized in that, the pressure range of described pressure filtration operation is 1~2.5atm.
7. press claims 1 described large-scale preparation method for amino borane, it is characterized in that, the vacuum tightness of described vacuum-evaporation operation is 0~0.098MPa, and temperature is-5~100 ℃.
8. press claims 1 described large-scale preparation method for amino borane, it is characterized in that, described vacuum-drying service temperature is 0~100 ℃.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102173385A (en) * | 2011-01-21 | 2011-09-07 | 南开大学 | Method for synthesizing high-capacity solid hydrogen storage material ammonia borane by using amino complex |
CN110550639A (en) * | 2019-07-24 | 2019-12-10 | 北京玻钢院复合材料有限公司 | Method for preparing borazine |
CN112010320A (en) * | 2020-08-12 | 2020-12-01 | 河南师范大学 | Preparation method of B-substituted sodium cyanoborohydride |
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DE4441064C1 (en) * | 1994-11-18 | 1996-07-18 | Metallgesellschaft Ag | Process for the preparation of alkali aminoborohydrides and alkali aminoborohydride complexes and their use |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102173385A (en) * | 2011-01-21 | 2011-09-07 | 南开大学 | Method for synthesizing high-capacity solid hydrogen storage material ammonia borane by using amino complex |
CN102173385B (en) * | 2011-01-21 | 2012-11-14 | 南开大学 | Method for synthesizing high-capacity solid hydrogen storage material ammonia borane by using amino complex |
CN110550639A (en) * | 2019-07-24 | 2019-12-10 | 北京玻钢院复合材料有限公司 | Method for preparing borazine |
CN110550639B (en) * | 2019-07-24 | 2021-03-09 | 北京玻钢院复合材料有限公司 | Method for preparing borazine |
CN112010320A (en) * | 2020-08-12 | 2020-12-01 | 河南师范大学 | Preparation method of B-substituted sodium cyanoborohydride |
CN112010320B (en) * | 2020-08-12 | 2023-05-23 | 河南师范大学 | Preparation method of B-substituted cyano sodium borohydride |
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