CN109970030A - A kind of synthesis technology of α-three aluminum hydride - Google Patents
A kind of synthesis technology of α-three aluminum hydride Download PDFInfo
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- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/06—Hydrides of aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth or polonium; Monoborane; Diborane; Addition complexes thereof
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Abstract
The invention belongs to hydrogen storage material technical fields, and in particular to a kind of synthesis technology of α-three aluminum hydride.The present invention provides a kind of preparation method of three aluminum hydrides, and ether solvent used in synthesis can directly recycle reuse without distillation process, reduces the cost of raw material of α-three aluminum hydride.The ether solvent of recycling can directly recycle reuse without distillation process, and α-three aluminum hydride reduced takes off the energy consumption level of ether crystallization reaction process.
Description
Technical field
The invention belongs to hydrogen storage material technical fields, and in particular to a kind of synthesis technology of α-three aluminum hydride.
Background technique
α-three aluminum hydride (α-AlH3), it is binary covalent hydride, volume hydrogen storage is 0.148kg H2(the 2 of liquid hydrogen density /L
It is more again), quality hydrogen storage reaches 10.08%, and hydrogen storage content with higher can be applicable to propellant, explosive, reducing agent, hydrogen fuel
Battery, technique for atomic layer deposition etc..Three aluminum hydrides have heterogeneity, and three non-solvated aluminum hydrides have seven kinds of different crystalline substances
Type, i.e. α-AlH3、β-AlH3、γ-AlH3、δ-AlH3、ε-AlH3、θ-AlH3、α’-AlH3, wherein three aluminum hydrides are with α-AlH3、β-
AlH3And γ-AlH3Based on the presence of three kinds of crystal forms, in this seven kinds of crystal forms, α-AlH3With most stable of structure, in air
In can be stabilized.α-the AlH of current practicability3Synthetic method (Preparation and based on " wet process " synthesis
Properties of Aluminum Hydride, Journal of the American Chemical Society, 1976,
Pp.2450-2453), i.e., suitable LiAlH4And AlCl3
3LiAlH4+AlCl3→4AlH3·nEt2O+3LiCl (1)
AlH3·nEt2O→AlH3+nEt2O (2)
It is reacted in diethyl ether solution, three aluminum hydride etherates (1) is generated, then in the nonpolar solvent of higher
The de- ether crystallization that flows back in (toluene, dimethylbenzene etc.) forms (2).The three aluminum hydride etherate of intermediate generated in this method exists
It is easy blocking reaction unit is precipitated in crystallization pipeline, valve in solvent ether, therefore is needed in synthesis molten using a large amount of ether
Agent maintains it in dissolved state.The solubility of three aluminum hydride etherate of intermediate reduces as the temperature rises, needs
To use cryogenic refrigeration equipment that solution low temperature (- 15 DEG C~-10 DEG C) is kept to be in three aluminum hydride etherates after filtration
Dissolved state, therefore the reaction process need to configure cryogenic refrigeration equipment, synthesis process energy consumption is larger.Due to AlH3Etherate
Solubility is limited in ether, leads to the single batch low output of the compound, while steaming solvent ether during de- ether
Distillation is gone, and a large amount of energy of process consuming leads to the synthesis process, and energy consumption is high.Document (Preparation,
characterization and decomposition ofγ-andα-alane AlH3, AIAA 2011-5583) and it reports and incites somebody to action
The AlH of preparation3Ether in etherate solution is evaporated at reduced pressure conditions, obtained three aluminum hydride etherate of solid-state
Solid phase is carried out after ground processing in vacuum drying oven or toluene and takes off ether, special ether is needed to be distilled to recover dress in this method
It sets and decompression vacuum pumping device, while solid AlH3Etherate solid powder needs milled processed to be easy during processing
Kindling causes the security risk of this method higher.Therefore a kind of reductions α-three aluminum hydride Preparation equipment cost of investment, reduction are developed
The energy consumption level of α-three aluminum hydride synthesis process and the synthesis technology of promotion α-three aluminum hydride synthesis process security risk are for α-
Three aluminum hydride large scale preparations and application have great significance.
Summary of the invention
Technology of the invention solves the problems, such as: overcoming the above-mentioned deficiency of the prior art, provides a kind of conjunction of α-three aluminum hydride
At technique, the synthesis technology of three aluminum hydride overcomes three aluminum hydride etherate of intermediate and is easy to be precipitated and use a large amount of
Ether solvent problem does not need the cryogenic refrigerating unit configured to keep the dissolution of three aluminum hydride etherates, reduces
The equipment cost of the reaction process and the energy consumption level of synthesis process, the ether solvent of recycling can be returned directly without distillation process
It receives and reuses, α-three aluminum hydride reduced takes off the energy consumption level of ether crystallization reaction process, while the synthesis technology improves
α-three aluminum hydride single batch of yield.
The technical solution of the invention is as follows:
A kind of the step of synthesis technology of α-three aluminum hydride, the technique includes:
(1) diethyl ether solution of the diethyl ether solution of aluminum trichloride (anhydrous) and lithium aluminium hydride reduction is mixed, is reacted, reacted
It is protected in the process using inert gas, reaction temperature is -10 DEG C -0 DEG C, is stirred in reaction process, and the reaction time is
30-60min；Inert gas is nitrogen, obtains mixture after reaction；Mixing speed is that 30-80 turns/min；
(2) mixture that step (1) obtains is filtered, removes filter cake, filter cake is side product chlorinated lithium；
(3) filtrate that step (2) obtains is heated, filtrate is stirred in heating process or ultrasonic, heating
Temperature is 10~25 DEG C, heating time 20-40min, obtains three aluminum hydride etherate slurries, is stood, and is divided after standing
Layer, upper layer is ether solvent, and it is reusable that ether solvent is transferred to reaction flask；Mixing speed is that 30-80 turns/min；
(4) lower layer's product that step (3) obtains is delivered in 82-88 DEG C of toluene and carries out de- ether precipitation, filtering will filter
Then cake makes to be washed with distilled water to be washed using ether, α-three aluminum hydride is dried to obtain after the completion of washing；
In the step (1), in the diethyl ether solution of aluminum trichloride (anhydrous), the volume and nothing of the anhydrous ether solvent of addition
The molar ratio of water alchlor is 0.4L~0.6L:1mol；
In the diethyl ether solution of lithium aluminium hydride reduction, the volume of the anhydrous ether solvent of addition and the molar ratio of lithium aluminium hydride reduction are 0.3L
~0.7L:1mol；The molar ratio of lithium aluminium hydride reduction and aluminum trichloride (anhydrous) is 3.2-4:1；
In the step (3), ultrasonic power is 100~500W；
In the step (4), the molar ratio of aluminum trichloride (anhydrous) is 0.5~0.8L in the volume of toluene and step (1):
1mol。
Compared with prior art, the present invention has the following advantages:
(1) present invention provides a kind of preparation method of three aluminum hydrides, and ether solvent used in synthesis can be without distillation
Process directly recycles reuse, reduces the cost of raw material of α-three aluminum hydride.The ether solvent of recycling is without distillation process
Reuse can be directly recycled, α-three aluminum hydride reduced takes off the energy consumption level of ether crystallization reaction process.
(2) synthesis process does not have to that three aluminum hydride etherate intermediates is kept to be in dissolution clear state, no
With using the cryogenic refrigeration equipment of energy consumption to keep the temperature it, the equipment cost and energy consumption level of the synthesis technology are reduced.
(3) technical process can increase LiAlH4And AlCl3Unit volume inventory, can under identical appointed condition
Promote single batch of yield of three aluminum hydrides.
(4) alchlor diethyl ether solution and lithium aluminium hydride reduction diethyl ether solution are mixed with the complexing of three aluminum hydride ether by the present invention
Object solution is filtered to remove side product chlorinated lithium, and filtrate is warming up to 10~25 DEG C and forms three hydrogenations under stirring or ultrasound condition
Ether is transferred to reaction flask after standing and reused, then hydrogenates remaining pulpous state three by aluminium etherate pulpous state system
Aluminium etherate, which is delivered in the toluene of high temperature, carries out de- ether precipitation, washes solid particle by distilled water, ethyl alcohol after filtering
α-three aluminum hydride product is dried to obtain after washing processing.The present invention can promote single batch of production of three aluminum hydrides under identical appointed condition
Amount.Ether solvent used in synthesis can directly recycle reuse without distillation process, reduce the original of α-three aluminum hydride
Material cost.Three hydrogenation aluminium complex diethyl ether solutions are kept the temperature without the cryogenic refrigeration equipment using energy consumption, reduce this
The equipment cost and energy consumption level of synthesis technology.
Specific embodiment
Embodiment 1
45 grams of lithium aluminium hydride reductions are dissolved in 0.38L anhydrous ether, by 48 grams of AlCl3It is dissolved in 0.15L anhydrous ether, leads to nitrogen and protects
It protects, is mixed 30 minutes under the conditions of -10 DEG C by alchlor diethyl ether solution and by lithium aluminium hydride reduction diethyl ether solution, after stopping reaction
It is filtered to remove side product chlorinated lithium, filtrate is warming up to 15 DEG C of three aluminum hydride ether complexing under 30 revs/min of stirring condition
Object slurry stops stirring after twenty minutes, the upper layer 0.37L ether solvent is shifted after standing, by remaining three aluminum hydrides ether network
Conjunction object slurry, which is transferred in 82 DEG C of 0.19L toluene, carries out de- ether, until the ether of condenser frozen-free will reaction after distillating
System is down to room temperature, is filtered, and then carries out distilled water, ethanol washing processing, obtains 30.6 grams of α-three aluminum hydrides after dry
Product.
Embodiment 2
49 grams of lithium aluminium hydride reductions are dissolved in 0.65L anhydrous ether, by 48 grams of AlCl3It is dissolved in 0.18L anhydrous ether, leads to nitrogen and protects
It protects, is mixed 40 minutes under the conditions of -8 DEG C by alchlor diethyl ether solution and by lithium aluminium hydride reduction diethyl ether solution, after stopping reaction
It is filtered to remove side product chlorinated lithium, filtrate is warming up to 10 DEG C of three aluminum hydride ether complexing under 50 revs/min of stirring condition
Object slurry stops stirring, shifts the upper layer 0.57L ether solvent after standing after 30 minutes.By remaining three aluminum hydrides ether network
Conjunction object slurry, which is transferred in 84 DEG C of 0.19L toluene, carries out de- ether, until the ether of condenser frozen-free will reaction after distillating
System is down to room temperature, is filtered, and then carries out distilled water, ethanol washing processing, obtains 31.6 grams of α-three aluminum hydrides after dry
Product.
Embodiment 3
52 grams of lithium aluminium hydride reductions are dissolved in 0.82L anhydrous ether, by 48 grams of AlCl3It is dissolved in 0.2L anhydrous ether, leads to nitrogen and protects
It protects, is mixed 45 minutes under the conditions of -5 DEG C by alchlor diethyl ether solution and by lithium aluminium hydride reduction diethyl ether solution, after stopping reaction
It is filtered to remove side product chlorinated lithium, filtrate is warming up to 20 DEG C of three aluminum hydride ether complexing under 80 revs/min of stirring condition
Object slurry stops stirring after forty minutes, shifts the upper layer 0.87L ether solvent after standing.By remaining three aluminum hydrides ether network
Conjunction object slurry, which is transferred in 86 DEG C of 0.25L toluene, carries out de- ether, until the ether of condenser frozen-free will reaction after distillating
System is down to room temperature, is filtered, and then carries out distilled water, ethanol washing processing, obtains 31.4 grams of α-three aluminum hydrides after dry
Product.
Embodiment 4
54 grams of lithium aluminium hydride reductions are dissolved in 0.95L anhydrous ether, by 48 grams of AlCl3It is dissolved in 0.21L anhydrous ether, leads to nitrogen and protects
It protects, is mixed 50 minutes under the conditions of -3 DEG C by alchlor diethyl ether solution and by lithium aluminium hydride reduction diethyl ether solution, after stopping reaction
It is filtered to remove side product chlorinated lithium, filtrate is warming up to 25 DEG C of three aluminum hydride etherate pulpous state under 100W ultrasound condition
Object stops ultrasound, shifts the upper layer 0.95L ether solvent after standing after 30 minutes.Remaining three aluminum hydrides etherate is starched
Shape object, which is transferred in 87 DEG C of 0.28L toluene, carries out de- ether, until the ether of condenser frozen-free drops reaction system after distillating
It to room temperature, is filtered, then carries out distilled water, ethanol washing processing, obtain 32.3 grams of α-three aluminum hydride products after dry.
Embodiment 5
46 grams of lithium aluminium hydride reductions are dissolved in 0.61L anhydrous ether, by 48 grams of AlCl3It is dissolved in 0.18L anhydrous ether, leads to nitrogen and protects
It protects, is mixed 60 minutes under the conditions of -1 DEG C by alchlor diethyl ether solution and by lithium aluminium hydride reduction diethyl ether solution, after stopping reaction
It is filtered to remove side product chlorinated lithium, filtrate is warming up to 20 DEG C of three aluminum hydride ether network under ultrasound condition under 400W ultrasound condition
Object slurry is closed, stops ultrasound after twenty minutes, shifts the upper layer 0.64L ether solvent after standing.By remaining three aluminum hydrides ether
Complex compound slurry, which is transferred in 88 DEG C of 0.25L toluene, carries out de- ether, until the ether of condenser frozen-free will be anti-after distillating
It answers system to be down to room temperature, is filtered, then carry out distilled water, ethanol washing processing, obtain 31 grams of α-three aluminum hydrides after dry
Product.
Claims (10)
1. a kind of synthesis technology of α-three aluminum hydride, it is characterised in that the step of technique includes:
(1) diethyl ether solution of the diethyl ether solution of aluminum trichloride (anhydrous) and lithium aluminium hydride reduction is carried out mixing to react, reaction terminates
After obtain mixture；
(2) mixture that step (1) obtains is filtered, removes filter cake, filtrate is heated, three aluminum hydride ether are obtained
Complex compound slurry is stood；
(3) lower layer's product that step (2) obtains is delivered in toluene and carries out de- ether precipitation, filter cake is used distilled water by filtering
Then washing is washed using ether, α-three aluminum hydride is dried to obtain after the completion of washing.
2. a kind of synthesis technology of α-three aluminum hydride according to claim 1, it is characterised in that: in the step (1),
It is protected in reaction process using inert gas.
3. a kind of synthesis technology of α-three aluminum hydride according to claim 1, it is characterised in that: in the step (1),
Reaction temperature is -10 DEG C -0 DEG C, reaction time 30-60min.
4. a kind of synthesis technology of α-three aluminum hydride according to claim 3, it is characterised in that: in the step (1),
It is stirred in reaction process, mixing speed is that 30-80 turns/min.
5. a kind of synthesis technology of α-three aluminum hydride according to claim 1, it is characterised in that: in the step (1),
In the diethyl ether solution of aluminum trichloride (anhydrous), the volume of the anhydrous ether solvent of addition and the molar ratio of aluminum trichloride (anhydrous) are 0.4L
~0.6L:1mol.
6. a kind of synthesis technology of α-three aluminum hydride according to claim 1, it is characterised in that: in the step (1),
In the diethyl ether solution of lithium aluminium hydride reduction, the volume of the anhydrous ether solvent of addition and the molar ratio of lithium aluminium hydride reduction are 0.3L~0.7L:
1mol；The molar ratio of lithium aluminium hydride reduction and aluminum trichloride (anhydrous) is 3.2-4:1.
7. a kind of synthesis technology of α-three aluminum hydride according to claim 1, it is characterised in that: in the step (2),
Carrying out heating temperature to filtrate is 10~25 DEG C, heating time 20-40min, filtrate is stirred in heating process or
Ultrasound.
8. a kind of synthesis technology of α-three aluminum hydride according to claim 7, it is characterised in that: in the step (2),
Mixing speed is that 30-80 turns/min.
9. a kind of synthesis technology of α-three aluminum hydride according to claim 7, it is characterised in that: in the step (3),
Ultrasonic power is 100~500W.
10. a kind of synthesis technology of α-three aluminum hydride according to claim 1, it is characterised in that: the step (4)
In, the molar ratio of aluminum trichloride (anhydrous) is 0.5~0.8L:1mol in the volume of toluene and step (1), and the temperature of toluene is 82-
88℃。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734053A (en) * | 2019-03-26 | 2019-05-10 | 哈尔滨工业大学 | A kind of three aluminum hydride preparation methods based on recycling ether solvent |
| CN114180522A (en) * | 2021-12-30 | 2022-03-15 | 北京珺政慧通科技有限公司 | Method for controlling particle size of alpha-aluminum trihydride |
| CN116477575A (en) * | 2023-03-09 | 2023-07-25 | 西安近代化学研究所 | alpha-AlH 3 Method for preparing the same |
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| CN106335877A (en) * | 2015-09-17 | 2017-01-18 | 湖北航天化学技术研究所 | Synthesis method of fine-grained alpha-AlH3 |
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| CN106335877A (en) * | 2015-09-17 | 2017-01-18 | 湖北航天化学技术研究所 | Synthesis method of fine-grained alpha-AlH3 |
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| T. KATO ET AL.: "Thermal properties of AlH3-etherate and its desolvation reaction into AlH3", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734053A (en) * | 2019-03-26 | 2019-05-10 | 哈尔滨工业大学 | A kind of three aluminum hydride preparation methods based on recycling ether solvent |
| CN114180522A (en) * | 2021-12-30 | 2022-03-15 | 北京珺政慧通科技有限公司 | Method for controlling particle size of alpha-aluminum trihydride |
| CN116477575A (en) * | 2023-03-09 | 2023-07-25 | 西安近代化学研究所 | alpha-AlH 3 Method for preparing the same |
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