CN102556970B - Preparation method for metallic amido-borane - Google Patents
Preparation method for metallic amido-borane Download PDFInfo
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- 229910000085 borane Inorganic materials 0.000 title claims abstract description 37
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 238000000498 ball milling Methods 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- -1 amino compound Chemical class 0.000 claims abstract description 7
- 229910052987 metal hydride Inorganic materials 0.000 claims abstract description 6
- 150000004681 metal hydrides Chemical class 0.000 claims abstract description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical group [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 claims description 9
- 150000002431 hydrogen Chemical group 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 7
- 229910000102 alkali metal hydride Inorganic materials 0.000 claims description 6
- 150000008046 alkali metal hydrides Chemical class 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- TVJORGWKNPGCDW-UHFFFAOYSA-N aminoboron Chemical compound N[B] TVJORGWKNPGCDW-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 claims description 2
- 238000013094 purity test Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 238000005119 centrifugation Methods 0.000 claims 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims 1
- 239000005695 Ammonium acetate Substances 0.000 claims 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims 1
- 229940043376 ammonium acetate Drugs 0.000 claims 1
- 235000019257 ammonium acetate Nutrition 0.000 claims 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims 1
- 235000019270 ammonium chloride Nutrition 0.000 claims 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims 1
- 235000011130 ammonium sulphate Nutrition 0.000 claims 1
- SPRIOUNJHPCKPV-UHFFFAOYSA-N hydridoaluminium Chemical compound [AlH] SPRIOUNJHPCKPV-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 235000002639 sodium chloride Nutrition 0.000 claims 1
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical group C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 claims 1
- 229910000045 transition metal hydride Inorganic materials 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 8
- 238000003860 storage Methods 0.000 abstract description 8
- 150000004678 hydrides Chemical class 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- 150000003624 transition metals Chemical class 0.000 abstract description 2
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 abstract 2
- 238000009825 accumulation Methods 0.000 abstract 1
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000001360 synchronised effect Effects 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 32
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 26
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 16
- 229910021529 ammonia Inorganic materials 0.000 description 13
- 229910000103 lithium hydride Inorganic materials 0.000 description 10
- 238000000634 powder X-ray diffraction Methods 0.000 description 10
- 239000011575 calcium Substances 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- SCCVHAICFFFJRA-UHFFFAOYSA-N [Li].NB Chemical compound [Li].NB SCCVHAICFFFJRA-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 238000010025 steaming Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000007039 two-step reaction Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 238000012857 repacking Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 208000035126 Facies Diseases 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000013872 defecation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 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 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OVTPXXUGQNROJL-UHFFFAOYSA-N [Na].BN Chemical compound [Na].BN OVTPXXUGQNROJL-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- BGECDVWSWDRFSP-UHFFFAOYSA-N borazine Chemical compound B1NBNBN1 BGECDVWSWDRFSP-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000002508 compound effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
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- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
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Abstract
The invention provides a low-cost preparation method for metallic amido-borane (M(NH2BH3)x.yNH3, wherein M is at least one element of alkali metal, alkaline-earth metal, transition metal or Al, x is 1, 2, 3 or 4 and y is 0-3. According to the low-cost preparation method, due to the adoption of a temperature-controlled ball milling technology, corresponding metal hydride or a metal amino compound, a hydroboron compound, ammonium salts and an organic solvent are fed into a ball milling tank according to a certain stoichiometric proportion; and the generation speed of an ammonia borane intermediate is controlled by precisely controlling the ball milling temperature. Therefore, the subsequent action between the ammonia borane and the hydride and the final decomposition of the metallic amido-borane as an object product due to excessive reaction heat accumulation caused by excessive intenseness can be avoided. According to the low-cost preparation method, noble amido-borane is prevented from serving as a raw material and two steps of reaction are combined into one step of reaction; meanwhile, an exothermic reaction between the amido-borane and the hydride is fully utilized and serves the reaction of the hydroboron and the ammonium salts, so that the metallic amido-borane is synchronized at low cost and the foundation for practical application of a high-capacity hydrogen storage system is laid.
Description
Technical field
The present invention relates to the technology of preparing of metallic amido-borane, be specially synthetic metallic amido-borane one preparation method is cheaply provided.
Background technology
The crude oil crisis that the world today is increasingly serious and environmental problem are Hydrogen Energy---a kind of generally acknowledged lustration type future source of energy provides fabulous development opportunity.The core technology in Hydrogen Energy field mainly comprises preparation, storage, transportation and the trans-utilization of hydrogen, and storage hydrogen is current research focus as the indispensable technology of the following mobile Hydrogen Energy device of development (as hydrogen fuel cell automobile), especially Ge great motor corporation drops into a lot of in hydrogen storage technology research and development.American energy office has formulated very harsh practical standard for vehicle-mounted hydrogen storage system simultaneously, comprises using high power capacity storage hydrogen material cheaply, reaches 6.5% system weight energy density; The suction hydrogen discharging temperature and all respects such as susceptibility and security of material to environment that adapt with Proton Exchange Membrane Fuel Cells.In recent years, increasingly complete along with fuel cell technology, becomes more urgent to the demand of storage hydrogen (hydrogen source) system.Will in the promotion of automobile industry and other energy industry be issued to ultimate attainment to seeking of novel high-capacity hydrogen storage material future.
Metallic amido-borane is as a kind of ammonia borine (NH of new report
3bH
3) derivative, because thering is high hydrogen weight density, compared with low pyrolysis desorption temperature and good dehydrogenation kinetics and paid close attention to.Chen Ping study group takes the lead in having synthesized lithium base, sodium base amino borane (LiNH by alkalimetal hydride and ammonia borine solid phase mechanical ball milling the earliest
2bH
3and NaNH
2bH
3), and its structure is resolved.Its building-up reactions formula is as follows:
LiH+NH
3BH
3→LiNH
2BH
3+H
2
NaH+NH
3BH
3→NaNH
2BH
3+H
2
At the beginning of achievement in research 2008, be published in " Nature Materials " upper, cause the great attention of storage hydrogen industry.With ammonia borine (NH
3bH
3) compare LiNH
2bH
3and NaNH
2bH
3not only can discharge respectively the hydrogen of 10.9% and 7.5% (weight ratio) at 91 ℃, and not produce the volatile byproducts murder by poisoning fuel cells such as borazine.What is more important, relatively more approaching the hankering property of the certain embodiments of metallic amido-borane on thermodynamics, though can not reversible suction hydrogen, can be in factory with compared with less energy-consumption again hydrogenation in off-board application.American energy office lists metallic amido-borane to approach in practical complex at present.Recently, Chen Ping study group synthesizes again potassium base amino borane (KNH
2bH
3), further enrich this material system.Simultaneously on synthesizing mean, for avoiding the separation problem of product and inertia grinding aid material in solid-phase ball milling preparation, Chen Ping team develops wet chemistry method synthesize metallic amido-borane.By by alkalimetal hydride and NH
3bH
3in tetrahydrofuran (THF) (THF) solution, act on, synthesize highly purified target product.In the practical process of hydrogen storage material, reduce the synthetic cost of material, simplify synthesizing mean and reach scale amplification being absolutely necessary.Adopt the preparation method of ammonia borine and hydride effect to only limit to scientific research scale, because ammonia borine price is up to 150 yuan/gram.And utilize sodium borohydride and volatile salt effect to prepare ammonia borine from tradition, at least face two-step reaction.
(NH
4)
2CO
3+2NaBH
4→Na
2CO
3+2NH
3BH
3+2H
2
LiH+NH
3BH
3→LiNH
2BH
3+H
2
Two-step reaction condition is not quite similar.The preparation of ammonia borine need be carried out at proper temperature, and itself and hydride or metal amino compound effects are an exothermic process, and temperature of reaction is too high slightly not control reaction scale, causes the pyrolysis of product metallic amido-borane.Mechanical ball milling can reduce reactant particle, improves two phase reaction interface, thereby guarantees to complete reaction process at lower temperature, avoids reacting thermal initiation product and decomposes.By temperature control solid-liquid ball milling, greatly reduce hydroborate and ammonium salt temperature of reaction, control ammonia borine generating rate, follow-up its further feeds back and promotes front step to react with the reaction heat of alkalimetal hydride effect.Two-step reaction merges a step in mechanical milling process, the building-up reactions formula as lithium amino borane:
(NH
4)
2CO
3+2NaBH
4+2LiH→Na
2CO
3+2LiNH
2BH
3+4H
2
The first step generates the certain temperature of process need of ammonia borine, the exothermic process that act as of second ammonia borine and alkalimetal hydride, and merging one step can realize heat complementation, guarantees temperature of reaction appropriateness, avoids the pyrolysis of product metallic amido-borane.
Summary of the invention:
The object of the invention is to provide the method for the synthetic metallic amido-borane of a kind of low cost.Particularly, adopt temperature control solid-liquid ball milling method reduce hydroborate and ammonium salt temperature of reaction and it and the effect of follow-up ammonia borine-alkalimetal hydride are carried out in the lump, utilize the heat complementation of two-step reaction process, realize next step synthetic metallic amido-borane of mild conditions, reduced preparation energy consumption.In addition, owing to avoiding using expensive ammonia borine for reacting initial thing, significantly reduced preparation cost.
The specific operation process that the present invention prepares metallic amido-borane is, by excessive metal hydride or metal amino compound and load weighted hydroborate, ammonium salt and quantitatively organic solvent are placed in steel ball grinder, insert 10 of 20 millimeters of Stainless Steel Balls of diameter simultaneously.After closed ball milling tank, moved to planetary ball mill, started ball milling preparation, accurately controlled ball milling chambers temp simultaneously.Via measuring ball grinder internal pressure reading, judge reacting finisheding degree.Until quantitative reaction finishes, discharge hydrogen in all tanks, white magma is transferred to tophan pot centrifugal treating.Isolated clear liquid part, through sucking filtering, guarantees to remove completely unreacted hydride residue, as at LiNH
2bH
3in preparation, lightweight lithium hydride cannot separate by centrifugal efficient, can only be by sucking filtering processing.On Rotary Evaporators, remove the organic solvent in clear liquid under reduced pressure, gained white crystals is metallic amido-borane.Purity testing is more than 95%.Because reaction mass amount is far above quantity of solvent, the supersaturation of target product metallic amido-borane is in organic solvent.Follow-up solid matter after centrifugal is reloaded to ball grinder, then add organic solvent to extract in room temperature, magma after ball milling is repeated to aforementioned operation, to improve product yield.Repeat twice extraction process and can obtain more than 91% yield.Concrete preparation flow is shown in that Fig. 1 is (with LiH and NaBH
4, (NH
4)
2cO
3raw material is example).
Adopt centrifugal and suction filtration technical finesse ball milling slurry, the solid product of separating reaction and unreacting material, suction filtration is mainly for being difficult for centrifugal lightweight material, as lithium hydride etc.
Prepared metallic amido-borane M (NH
2bH
3)
xyNH
3, wherein M is at least one element in basic metal, alkaline-earth metal, transition metal (as Li, Na, K, Ca, Mg, Sr, Ba, Ti, Co) or Al, x=1,2,3,4, y=0～3;
The required technique of basic metal ammonia borine synthetic method, equipment that the present invention proposes are very simple, and visual actual needs is adjusted industrial scale.Synthetic required reaction conditions gentleness, simultaneously can on-line monitoring level of response, and security of system is high.Organic solvent used can reuse to reduce costs and environmental pollution.By product hydrogen can be collected for hydride and prepare.
Accompanying drawing explanation:
Fig. 1. preparation technology's schema of metallic amido-borane.(lithium amino borane is abbreviated as LiAB)
Fig. 2. the X-ray powder diffraction figure of lithium amino borane.
Fig. 3. the X-ray powder diffraction figure of sodium amino borane.
Fig. 4. the X-ray powder diffraction figure of calcium amino borane-ammonia.
Specific embodiment:
The present invention is by the mode one-step synthesis metallic amido-borane of temperature control ball milling, concrete synthesis flow as shown in Figure 1, to synthesize lithium amino borane as example.Other raw materials also adopt identical flow process.By implementation column, the present invention is described in detail below, but the present invention is not limited to these embodiment.
Embodiment 1:
19 grams of NaBH
4(NH with 28.8 grams
4)
2cO
3(slightly excessive), the LiH (excessive) of 8 grams and 500 milliliters of THF together add in the steel ball grinder of 2 liters, and cover is equipped with opening-closing valve and is convenient to Bonding pressure sensor detecting tank internal pressure.Close after cover, place ball grinder in the heatable Retsch PM400 planetary ball mill of a repacking, after body inner chamber is warming up to 30 ℃, start ball milling program, record tank internal pressure after moving 5 hours under rotating speed 110rpm and reach desired value, indicating finishing of reaction.In toilet-cleaning jar, after hydrogen, pump thick the slurry to tophan pot of white in tank.Under 3000rpm rotating speed, centrifugal treating is found after 30 minutes to still have suspended solids in supernatant liquid, and therefore by clear liquid sucking filtering, suspended solids is unreacted lightweight LiH particle.Principal defecation liquid, through underpressure distillation, distillates THF, and the white crystals obtaining proves LiNH through X-ray powder diffraction test
2bH
3, as shown in Figure 2, it is more than 95% that X-ray powder diffraction picture analysis obtains its purity.By twice 500 milliliters of THF extraction, centrifugal suction filtration and revolve steaming, receives to obtain LiNH
2bH
316.8 grams of solids, yield is 91%.
Embodiment 2:
By 0.003mol NaBH
4(1.14 grams), 0.002mol (NH
4)
2cO
3(1.92 grams), 0.006mol LiH (0.48 gram) and 30 milliliters of THF together add in autoclave, rapid stirring 10 hours at 30 ℃, it is 20psi that the pressure transmitter of ligation still records still internal pressure, is only equivalent to 10% reaction completeness.X-ray powder diffraction characterizes solid residue in still, finds still to have very strong NaBH
4(NH
4)
2cO
3diffracted signal, this shows that under above-mentioned experiment condition chemical action is between the two very weak.In addition, in solid, detected a small amount of LiNH
2bH
3generating, is NH
3bH
3with the follow-up exercising result of LiH.Rising autoclave temperature of reaction to 50 ℃, more hydrogen is released, NaBH
4(NH
4)
2cO
3effect is obviously strengthened, but in reaction product, does not find more LiNH
2bH
3.Know LiNH from bibliographical information
2bH
3in THF, at 50 ℃, decompose, degradation production is amorphous.Therefore, traditional stirring reaction is to promote reaction to carry out in the time of rising temperature of reaction, but is difficult to avoid the decomposition of product.As a comparison, adopt temperature control ball milling method to implement above-mentioned example, reaction can complete in short 4 hours, and pressure reaches predictor.In tank, in residual solids, NaBH4 detected, major ingredient is unreacted LiH, product LiNH
2bH
3and a small amount of (NH
4)
2cO
3.
Embodiment 3
19 grams of NaBH
4(NH with 28.8 grams
4)
2cO
3(slightly excessive), the KH (excessive) of 28 grams and 500 milliliters of THF together add in the steel ball grinder of 2 liters, and cover is equipped with opening-closing valve and is convenient to Bonding pressure sensor detecting tank internal pressure.Close after cover, place ball grinder in the heatable Retsch PM400 planetary ball mill of a repacking, after body inner chamber is warming up to 30 ℃, start ball milling program, record tank internal pressure after moving 5.5 hours under rotating speed 110rpm and reach desired value, indicating finishing of reaction.In toilet-cleaning jar, after hydrogen, pump thick the slurry to tophan pot of white in tank.Under 3000rpm rotating speed, centrifugal treating finds after 30 minutes that supernatant liquid clarifies, and unreacted KH particle has been centrifuged to bottom.Principal defecation liquid is through underpressure distillation, and the white crystals obtaining, proves KNH through X-ray powder diffraction
2bH
3, it is more than 90% that facies analysis obtains its purity.By twice 500 milliliters of THF extraction, centrifugal suction filtration and revolve steaming, receives to obtain KNH
2bH
334.5 grams of solids, yield is 85%.
Embodiment 4
19 grams of NaBH
4nH with 32.04 grams
4cl (slightly excessive), the NaH (excessive) of 16.8 grams and 500 milliliters of THF together add in the steel ball grinder of 2 liters, and cover is equipped with opening-closing valve and is convenient to Bonding pressure sensor detecting tank internal pressure.Close after cover, place ball grinder in the heatable Retsch PM400 planetary ball mill of a repacking, after body inner chamber is warming up to 30 ℃, start ball milling program, record tank internal pressure after moving 5 hours under rotating speed 110rpm and reach desired value, indicating finishing of reaction.In toilet-cleaning jar, after hydrogen, pump thick the slurry to tophan pot of white in tank.Under 3000rpm rotating speed, centrifugal treating finds after 30 minutes that supernatant liquid clarifies substantially, and clear liquor, through underpressure distillation, distillates THF, and the white crystals obtaining proves NaNH through X-ray powder diffraction
2bH
3, as shown in Figure 3, it is more than 85% that facies analysis obtains its purity.By twice 500 milliliters of THF extraction, centrifugal suction filtration and revolve steaming, receives to obtain NaNH
2bH
321.7 grams of solids, yield is 82%.
Embodiment 5
19 grams of NaBH
4(NH with 28.8 grams
4)
2cO
3(slightly excessive), 20gCa (NH
2)
2(excessive) and 500 milliliters of THF together add in the steel ball grinder of 2 liters, and cover is equipped with opening-closing valve and is convenient to Bonding pressure sensor detecting tank internal pressure.Close after cover, place ball grinder in a Retsch PM400 planetary ball mill, after room temperature (25 ℃) starts down ball milling program, moves 6 hours under rotating speed 110rpm, record tank internal pressure and reach desired value, indicating finishing of reaction.Due to the first step reaction (NH
4)
2cO
3+ 2NaBH
4→ Na
2cO
3+ 2NH
3bH
3+ 2H
2at room temperature deferred reaction, once there be NH
3bH
3generate, with Ca (NH
2)
2generation very exothermic reaction: Ca (NH
2)
2+ 2NH
3bH
3→ Ca (NH
2bH
3)
22NH
3, liberated heat accelerates the carrying out of the first step reaction, can realize like this without in the situation of indirect heating by initial feed one-step synthesis Ca (NH
2bH
3)
22NH
3.In toilet-cleaning jar, after hydrogen, pump thick the slurry to tophan pot of white in tank.Centrifugal treating 30 minutes under 3000rpm rotating speed, supernatant liquid, through underpressure distillation, distillates THF, and the white crystals obtaining proves Ca (NH through X-ray powder diffraction test
2bH
3)
22NH
3, as shown in Figure 4, it is more than 90% that X-ray powder diffraction picture analysis obtains its purity.By twice 500 milliliters of THF extraction, centrifugal suction filtration and revolve steaming, receives to obtain Ca (NH
2bH
3)
22NH
328.5 grams of solids, yield is 85%.
Claims (10)
1. the preparation method of a metallic amido-borane, it is characterized in that: adopt temperature control ball grinding technique, by corresponding metal hydride or metal amino compound and hydroborate, ammonium salt and organic solvent are dosed in ball grinder in the lump by stoicheiometry, the accurate ball milling temperature and time of controlling, subsequent ball milling slurry is gone through centrifugation and/or sucking filtering, gained clear liquid is again via underpressure distillation the dry gained solid of finding time, finally obtain high purity metal amino borane, the purity testing of described high purity metal amino borane is more than 95%;
The mol ratio of metal hydride or metal amino compound, hydroborate, ammonium salt, organic solvent is: 0.5～2.5:0.3～3:1:5～12, ball milling chambers temp scope is 0～100 ℃, because one of reaction product is hydrogen, can calculate the amount of hydrogen after complete reaction according to material quantity, and then can calculate the pressure in ball sealer grinding jar while reacting end, therefore can determine Ball-milling Time by monitoring ball grinder internal pressure.
2. preparation method as claimed in claim 1, is characterized in that: described temperature control ball milling adopts the heatable ball mill in ball milling chamber.
3. preparation method as claimed in claim 1, is characterized in that: described metal hydride is one or two or more kinds in alkalimetal hydride, alkaline earth metal hydride, transition metal hydride or aluminum hydride, and metal amino compound is LiNH
2, NaNH
2, KNH
2, Mg (NH
2)
2, Ca (NH
2)
2, Sr(NH
2)
2in one or two or more kinds.
4. preparation method as claimed in claim 1, is characterized in that: described metal hydride is LiH, NaH, KH, MgH
2, CaH
2, SrH
2, BaH
2, TiH
2, AlH
3in one or two or more kinds.
5. preparation method as claimed in claim 1, is characterized in that: described hydroborate is LiBH
4, NaBH
4, KBH
4, Mg (BH
4)
2, Ca (BH
4)
2in one or two or more kinds.
6. preparation method as claimed in claim 1, is characterized in that: described ammonium salt is ammonium chloride, Neutral ammonium fluoride, ammonium sulfate, volatile salt, bicarbonate of ammonia or ammonium acetate.
7. preparation method as claimed in claim 1, is characterized in that: described organic solvent is tetrahydrofuran THF or ether.
8. preparation method as claimed in claim 1, is characterized in that: adopt planetary ball mill ball milling, ball mill rotational speed of ball-mill scope is: 0～600rpm.
9. preparation method as claimed in claim 1, it is characterized in that: ball milling slurry is metallic amido-borane supersaturated solution, need repeat temperature control ball milling claimed in claim 1 and distillate the solid process that solvent and centrifugation go out, to obtain high product yield, the yield that described high product yield is 91%.
10. preparation method as claimed in claim 1, is characterized in that: reactant carries out building-up reactions in ball grinder;
Described ball grinder is airtight ball grinder, and the vapor pipe with valve is housed on the lid of ball grinder, can be connected with tensimeter, to monitor in real time tank internal pressure.
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| CN101746726A (en) * | 2008-12-08 | 2010-06-23 | 复旦大学 | A method for preparing pure LiNH2BH3, naNH2BH3 |
| CN101746728A (en) * | 2008-12-18 | 2010-06-23 | 复旦大学 | Preparation method of high purity LiNH2BH3, naNH2BH3 |
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| CN101746726A (en) * | 2008-12-08 | 2010-06-23 | 复旦大学 | A method for preparing pure LiNH2BH3, naNH2BH3 |
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