CN102219187A - Preparation method for calcium borohydride hydrogen-storage material - Google Patents
Preparation method for calcium borohydride hydrogen-storage material Download PDFInfo
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- CN102219187A CN102219187A CN2010101466104A CN201010146610A CN102219187A CN 102219187 A CN102219187 A CN 102219187A CN 2010101466104 A CN2010101466104 A CN 2010101466104A CN 201010146610 A CN201010146610 A CN 201010146610A CN 102219187 A CN102219187 A CN 102219187A
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- calcium
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- halogenide
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- organic solvent
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
Abstract
The invention discloses a preparation method for a calcium borohydride hydrogen-storage material, which comprises the following steps of: adding a calcium metal halide and a metal borohydride at a certain stoichiometric ratio into a pressure-resistant container and mechanically mixing or mechanically ball-milling for uniformly mixing; adding an appropriate amount of an organic solvent to the uniformly mixed reaction raw materials, stirring at room temperature for complete a replacement reaction of the calcium metal halide and metal borohydride; and separating reaction products as well as purifying and crystallizing to obtain calcium borohydride. The preparation method provided by the invention is simple to operate, has the advantages of low cost, easiness in mass production, high yield and the like, and can prepare high-purity products.
Description
Technical field
The present invention relates to hydrogen storage material, belong to the material technology preparation field, be specifically related to a kind of preparation method of hydroboration calcium hydrogen storage material.
Background technology
The energy is the basic substance that the mankind depend on for existence, and its main body mainly is non-renewable fossil resource at present, comprises coal, oil, Sweet natural gas etc.But, use fossil resource to bring problems such as serious energy scarcity and environmental pollution to the universe.Hydrogen has now become the emphasis direction of whole world research because its aboundresources, efficiency of combustion height, pollution-free etc. are considered to the secondary energy that ideal substitutes fossil resource.But a key factor that realizes " Hydrogen Energy economy " is research and development efficient, the reversible solid hydrogen storage material, and its technical indicator is that hydrogen storage capability reaches more than 6% (weight ratio).In the present all kinds of hydrogen storage alloy, AB
5(with LaNi
5Be representative) and AB
2(with TiMn
2Be representative) research and development ripe, but its hydrogen-storage amount has limited their practical application less than 2% (weight percent).Magnuminium has bigger hydrogen storage capability (MgH
2Hydrogen storage capability reach 7.6%), but the application requiring that hydrogen condition (temperature is more than 300 ℃) is difficult to satisfy fuel cell is equally put in the suction of its harshness.In recent years, metal borohydride more and more is subjected to people's attention with its high hydrogen richness, lithium borohydride (LiBH
4) be representational coordination metal borohydride, its weight hydrogen density is up to 18.4%.In recent years, the various countries scholar is around improving LiBH
4Comprehensive storage/the hydrogen discharging performance of material has been carried out a large amount of experiments/theoretical investigation work, substitutes aspects such as reaching the catalyst system structure at system composition/response path adjustment, nanostructure modulation, anion/cation and has obtained multinomial positive progress.
Alkaline-earth metal boron hydride as hydroboration calcium and magnesium borohydride, is the very promising hydrogen storage material of a class, becomes one of focus of hydrogen storage material area research in recent years.The hydrogen richness of hydroboration calcium is up to weight ratio 11.4%.At present alkaline-earth metal boron hydride (as hydroboration calcium and magnesium borohydride) mainly from prepared in laboratory, as: 1. prepare hydroboration calcium and need organic boride (Et
3NBH
3) react with hydrolith: used organic boride in the reaction, the cost of raw material is higher, and needs complicated backflow and drying and roasting process [M.D.Riktor, M.H.
K.
M.Fichtner, F.Buchter, A.Z ü ttel, B.C.Hauback, J.Mater.Chem., 2007,17:4939-4942.]; 2. utilize reaction CaB
6+ 2CaH
2+ 10H
2→ 3Ca (BH
4)
2Preparation, but need relatively harsher experiment condition, have catalyzer in the presence of still need 140 normal atmosphere [C.Rongeat, V.D ' Anna, H.Hagemann, A.Borgschulte, A.Z ü ttel, L.Schultz, O.Gutfleisch, J.AlloysCompd., 2010,493:281-287.] or 400 ℃ of high temperature [
Et al., Direct synthesisof calcium borohydride, US patent, 7,608,233; Ewa
Eric H.Majzoub, J.Phys.Chem.B, 2007,111:12045-12047.]; 3. adopt the mechanical ball milling method by replacement(metathesis)reaction 2LiBH
4+ CaCl
2→ Ca (BH
4)
2+ 2LiCl prepares, but can't separating by-products LiCl[Y.Nakamori, H.-W.Li, K.Kikuchi, M.Aoki, K.Miwa, S.Towata, S.Orimo, J.Alloys Compd., 2007,446-447:296-300.].Though commercial alkaline-earth metal boron hydride (hydroboration calcium and magnesium borohydride) is also arranged at present, price is extremely expensive, and for example the price of hydroboration calcium is up to arriving 1,500 yuans of every grams.This shows that in order further to study the hydrogen storage property of alkaline-earth metal boron hydride (hydroboration calcium and magnesium borohydride), reduce material cost, the novel method that develops low-cost feedstock production hydroboration calcium hydrogen storage material is extremely urgent.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of simple to operate, raw material is cheap and easy to get, product purity is high, yield is high hydroboration calcium hydrogen storage material.
It is raw material that the present invention proposes with metal borohydride and calcium halide, passes through replacement(metathesis)reaction: 2MBH
4+ CaX
2→ Ca (BH
4)
2+ 2MX (M=Li or Na, X=F, Cl, Br I), prepares required product C a (BH
4)
2
A kind of preparation method of hydroboration calcium hydrogen storage material comprises being prepared as follows step:
1) under the condition of secluding air, the mixture of the halogenide of calcium metal and metal borohydride to be packed in the pressure vessel, the addition of raw material makes in the mixture that the atomic ratio of calcium is 1～6 in the metal in the hydroborate and halogenide;
2) mode of employing mechanically mixing or mechanical ball milling mixes the halogenide of calcium metal and the mixture of metal borohydride, and to wherein adding organic solvent;
3) at room temperature, the organic solution of halogenide that calcium metal is housed and metal borohydride is carried out magnetic agitation or mechanical ball milling is handled;
4) under the condition of secluding air, with 3) solution that obtains filters or centrifugally operated, obtains clear filtrate after removing insoluble precipitate;
5) utilize Rotary Evaporators that clear filtrate is at room temperature carried out underpressure distillation and reclaim organic solvent, or directly under the vacuum organic solvent is removed, obtain white solid;
6) with 5) the white solid roasting that obtains, can obtain hydroboration calcium of the present invention; Maturing temperature is 160-250 ℃, and roasting time is 1-24 hour.
The halogenide of described alkaline earth metals calcium is CaF
2, CaCl
2, CaBr
2Or CaI
2, metal borohydride is LiBH
4, NaBH
4, KBH
4, Mg (BH
4)
2, Zn (BH
4)
2Or Ti (BH
4)
3
The halogenide of described alkaline earth metals calcium and metal borohydride combination are preferably LiBH
4And CaCl
2, or NaBH
4And CaCl
2
Step 2) and 3) described in the halogenide of alkaline earth metals calcium and alkali metal borohydride mix on powder machine, planetary ball mill, swing type ball mill or the oscillatory type ball mill at automation and carry out mechanically mixing or mechanical ball milling; The abrading-ball that is adopted during ball-milling processing is Stainless Steel Ball, zirconia ball or agate ball; Mechanically mixing or mechanical ball milling carry out under vacuum or inert atmosphere protection, and inert atmosphere is nitrogen atmosphere, argon atmospher or helium-atmosphere.
During ball milling, the weight ratio of abrading-ball and sample is (10-100): 1, and the planetary ball mill rotating speed is 50-500rpm, and the shimmy frequency of swing type ball mill is the 50-600 cycle per minute, and the rotating speed that mixes the powder machine automatically is 10-100rpm; Mechanical ball milling or blended time are 1-24 hour.
Described organic solvent is that tetrahydrofuran (THF), methyltetrahydrofuran, carbonatoms are the ether of C2-C6, as methyl ether, ether, methyl ethyl ether, isopropyl ether, methyl tertiary butyl ether, glycol dimethyl ether etc.; The addition of organic solvent is 10-300mL in every 1-2g hydroborate.Should guarantee there is not water before solvent uses, oxygen and with the impurity of raw material reaction.
Under the step 3) room temperature, the time of the special reactor of the halogenide that adds the alkaline earth metals calcium that being equipped with of an amount of organic solvent mix and metal borohydride being carried out magnetic agitation or ball-milling processing is 2 hours-48 hours.
Clear filtrate carried out underpressure distillation reclaim organic solvent, or the temperature of directly organic solvent being removed under the vacuum is 25-160 ℃ that the time is 30 minutes-5 hours.
The condition of secluding air is meant under vacuum or inert atmosphere protection carries out, and inert atmosphere is nitrogen atmosphere, argon atmospher or helium-atmosphere.
The present invention has following advantage:
1. the raw material that is adopted is the halogenide and the metal borohydride of alkaline earth metals calcium, and is rich and easy to get, cheap, greatly reduces the cost of product.
2. preparation process is simple, and easy handling control helps accomplishing scale production.
3. solved the separation problem of by product metal halide.
4. reaction product yield height.
5. impurity in products content is low, and purity is higher.
Description of drawings
Fig. 1 is for being the X ray diffracting spectrum of the by product sodium-chlor of feedstock production hydroboration calcium with calcium chloride and sodium borohydride.
Fig. 2 is for calcium chloride and sodium borohydride being the X ray diffracting spectrum of the hydroboration calcium (high temperature mutually with low temperature mixed phase mutually) of feedstock production.
Fig. 3 is for being the temperature programming dehydrogenation curve of the hydroboration calcium of feedstock production with calcium chloride and sodium borohydride.
Fig. 4 is for being the X ray diffracting spectrum of the hydroboration calcium (high temperature mutually) of feedstock production with calcium chloride and sodium borohydride.
Embodiment
Embodiment 1
In being full of the glove box of high-purity argon gas, take by weighing 1.73 gram calcium chloride and 1.16 gram sodium borohydrides respectively in ball grinder, argon shield, ball milling mixes on planetary ball mill, and ratio of grinding media to material is 100: 1, and rotating speed is 200rpm, and the ball milling time is 5 hours.Under the condition of secluding air, get said mixture in the 500mL round-bottomed flask, add 200 milliliters of tetrahydrofuran (THF)s then, leniently stirred under the room temperature 48 hours.The suspension liquid that obtains is removed by filter insolubles sodium-chlor, and X ray diffracting spectrum has only sodium-chlor as shown in Figure 1 in the solid reaction product, can't see the existence of raw material, and it is very complete to illustrate that reaction is carried out, and does not have the reactant residue, and by product is easy to separate.Filtrate underpressure distillation at room temperature removed desolvate, 230 ℃ of following vacuum bakings 5 hours, can obtain product hydroboration calcium then, yield can reach 92%.The X ray diffracting spectrum of product as shown in Figure 2, as can be seen from the figure, the hydroboration calcium that obtains be low temperature mutually and high temperature mixing mutually, do not have by product sodium-chlor, product purity is higher, can reach more than 95%.Its temperature programming dehydrogenation behavior at 480 ℃ of hydrogen that can discharge above 8wt%, is one of more promising hydrogen storage material as shown in Figure 3.
In being full of the glove box of high-purity argon gas, take by weighing 0.247 gram calcium chloride and 0.171 gram sodium borohydride respectively in ball grinder, add 30 milliliters of tetrahydrofuran (THF)s then; argon shield, ball milling mixes on planetary ball mill, and ratio of grinding media to material is 50: 1; rotating speed is 100rpm, and the ball milling time is 15 hours.Under the condition of secluding air, the suspension liquid that obtains is removed by filter insolubles sodium-chlor, the filtrate decompression distillation is removed desolvate, then 200 ℃ of following vacuum bakings 10 hours, adopt the process of slowly cooling to reduce to room temperature, can obtain the hydroboration calcium of the single high temperature phase of product, yield can reach 96%.The X ray diffracting spectrum of product as shown in Figure 4, no coupling product sodium-chlor, purity is higher, can reach more than 95%.
Claims (9)
1. the preparation method of a hydroboration calcium hydrogen storage material is characterized in that comprising being prepared as follows step:
1) under the condition of secluding air, the mixture of the halogenide of calcium metal and metal borohydride to be packed in the pressure vessel, the atomic ratio of calcium is 1～6 in metal in the mixture in the hydroborate and the halogenide;
2) mode of employing mechanically mixing or mechanical ball milling makes the halogenide of calcium metal and the mixture uniform mixing of metal borohydride, and adds organic solvent;
3) at room temperature, the organic solution of halogenide that calcium metal is housed and metal borohydride is carried out magnetic agitation or mechanical ball milling is handled;
4) under the condition of secluding air, with 3) solution that obtains filters or centrifugally operated, removes post precipitation and obtain clear filtrate;
5) utilize Rotary Evaporators that clear filtrate is at room temperature carried out underpressure distillation, or directly under the vacuum organic solvent is removed, obtain white solid;
6) with 5) the white solid roasting that obtains, can obtain hydroboration calcium of the present invention, maturing temperature is 160-250 ℃, roasting time is 1-24 hour.
2. according to the described preparation method of claim 1, it is characterized in that: the halogenide of described alkaline earth metals calcium is CaF
2, CaCl
2, CaBr
2Or CaI
2, metal borohydride is LiBH
4, NaBH
4, KBH
4, Mg (BH
4)
2, Zn (BH
4)
2Or Ti (BH
4)
3
3. according to the described preparation method of claim 1, it is characterized in that: the halid preferably combination of described metal borohydride and alkaline earth metals calcium is LiBH
4And CaCl
2, or NaBH
4And CaCl
2
4. according to the described preparation method of claim 1, it is characterized in that: step 2) and 3) described in the halogenide of alkaline earth metals calcium and alkali metal borohydride mix on powder machine, planetary ball mill, swing type ball mill or the oscillatory type ball mill at automation and carry out mechanically mixing or mechanical ball milling; The abrading-ball that is adopted during ball-milling processing is Stainless Steel Ball, zirconia ball or agate ball; Mechanically mixing or mechanical ball milling carry out under vacuum or inert atmosphere protection, and inert atmosphere is nitrogen atmosphere, argon atmospher or helium-atmosphere.
5. according to the described preparation method of claim 4, it is characterized in that: during ball milling, the weight ratio of abrading-ball and sample is (10-100): 1, and the planetary ball mill rotating speed is 50-500rpm, the shimmy frequency of swing type ball mill is the 50-600 cycle per minute, and the rotating speed that mixes the powder machine automatically is 10-100rpm; Mechanical ball milling or blended time are 1-24 hour.
6. according to the described preparation method of claim 1, it is characterized in that: described organic solvent is that tetrahydrofuran (THF), methyltetrahydrofuran, carbonatoms are the ether of C2-C6; The addition of organic solvent is 10-300mL in every 1-2g hydroborate.
7. according to the described preparation method of claim 1, it is characterized in that: in the step 3), at room temperature, the time that the special reactor of the halogenide that adds the alkaline earth metals calcium that being equipped with of an amount of organic solvent mix and metal borohydride is carried out magnetic agitation or ball-milling processing is 2 hours-48 hours.
8. according to the described preparation method of claim 1, it is characterized in that: clear filtrate is carried out underpressure distillation, or the temperature of directly organic solvent being removed under the vacuum is 25-160 ℃, the time is 30 minutes-5 hours.
9. according to the described preparation method of claim 1, it is characterized in that: the condition of secluding air is meant under vacuum or inert atmosphere protection carries out, and inert atmosphere is nitrogen atmosphere, argon atmospher or helium-atmosphere.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105417496A (en) * | 2014-09-23 | 2016-03-23 | 中国科学院大连化学物理研究所 | synthesis method for borohydride of sodium |
| CN106315512A (en) * | 2016-08-10 | 2017-01-11 | 南通南京大学材料工程技术研究院 | Method for inducing and synthesis gamma-Ca(BH4)2 through mechanical force |
| CN106744872A (en) * | 2016-12-01 | 2017-05-31 | 安徽工业大学 | A kind of preparation method of the multi-layer graphene nanometer sheet of the boron hydride that adulterates |
| CN107522165A (en) * | 2017-09-20 | 2017-12-29 | 庄英俊 | A kind of preparation method of lithium borohydride tetrahydrofuran solution |
| CN107601432A (en) * | 2017-09-29 | 2018-01-19 | 山东国邦药业股份有限公司 | A kind of method that potassium borohydride is prepared using potassium metaborate |
| CN108285130A (en) * | 2018-02-11 | 2018-07-17 | 庄英俊 | A kind of preparation method and detection method of lithium borohydride |
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| CN101074092A (en) * | 2006-05-19 | 2007-11-21 | 罗门哈斯公司 | Preparation of borohydride salts |
| US7608233B1 (en) * | 2007-02-12 | 2009-10-27 | Sandia Corporation | Direct synthesis of calcium borohydride |
-
2010
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Patent Citations (2)
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|---|---|---|---|---|
| CN101074092A (en) * | 2006-05-19 | 2007-11-21 | 罗门哈斯公司 | Preparation of borohydride salts |
| US7608233B1 (en) * | 2007-02-12 | 2009-10-27 | Sandia Corporation | Direct synthesis of calcium borohydride |
Non-Patent Citations (2)
| Title |
|---|
| 《International Journal of Hydrogen Energy》 20090210 Grigorii L.Soloveichik，et al. Magnesium borohydride as a hydrogen storage material: Synthesis of unsolvated Mg(BH4)2 2144-2152 1-9 第34卷, * |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105417496A (en) * | 2014-09-23 | 2016-03-23 | 中国科学院大连化学物理研究所 | synthesis method for borohydride of sodium |
| CN105417496B (en) * | 2014-09-23 | 2017-12-12 | 中国科学院大连化学物理研究所 | A kind of synthetic method of the hydroboron of sodium |
| CN106315512A (en) * | 2016-08-10 | 2017-01-11 | 南通南京大学材料工程技术研究院 | Method for inducing and synthesis gamma-Ca(BH4)2 through mechanical force |
| CN106744872A (en) * | 2016-12-01 | 2017-05-31 | 安徽工业大学 | A kind of preparation method of the multi-layer graphene nanometer sheet of the boron hydride that adulterates |
| CN107522165A (en) * | 2017-09-20 | 2017-12-29 | 庄英俊 | A kind of preparation method of lithium borohydride tetrahydrofuran solution |
| CN107601432A (en) * | 2017-09-29 | 2018-01-19 | 山东国邦药业股份有限公司 | A kind of method that potassium borohydride is prepared using potassium metaborate |
| CN108285130A (en) * | 2018-02-11 | 2018-07-17 | 庄英俊 | A kind of preparation method and detection method of lithium borohydride |
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Application publication date: 20111019 |