CN106946224B - The method for preparing α-three aluminum hydride with lithium aluminium hydride reduction and lithium borohydride mixed catalytic - Google Patents
The method for preparing α-three aluminum hydride with lithium aluminium hydride reduction and lithium borohydride mixed catalytic 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 discloses a kind of methods for preparing α-three aluminum hydride with lithium aluminium hydride reduction and lithium borohydride mixed catalytic, comprising the following steps: (1) preparation of mixed catalytic agent solution；(2) synthesis of α-three aluminum hydride；(3) product purification and drying.A kind of method preparing α-three aluminum hydride with lithium aluminium hydride reduction and lithium borohydride mixed catalytic provided by the invention, can carry out in normal pressure and compared under low reaction temperatures, and step is simple, and easily operated, device is simple, can be applied to industrialized production.The method of the present invention economical and efficient, production cost is low, and gained α-three aluminum hydride crystal form is single, and for product purity height up to 99.8%, stability is high, easily stored, chemical stability be conducive to energetic material, propellant and in terms of application.
Description
Technical field
The present invention relates to a kind of methods for preparing α-three aluminum hydride with lithium aluminium hydride reduction and lithium borohydride mixed catalytic, specific to belong to
In metal hydride preparation technical field.
Background technique
Currently, countries in the world are all in the synthetic work for being dedicated to high Energy Density Materials, but the work of this part is quite multiple
Miscellaneous and hard, Germany synthesizes hexogen (RDX) first within 1899, and octogen (HMX) is just found simultaneously until nineteen forty-one
It separates, HMX is used till today as the highest explosive of energy to equip our troops.Consider from present reality, to synthesize performance
Compound better than HMX simultaneously reaches the marketization, is difficult to make a breakthrough at no distant date.Therefore in suitable period from now on, HMX is still
It is so the highest explosive of energy to equip our troops, there are also quite a few ground Suppressed Weapons ammunition also mixing with RDX and TNT
It closes explosive and has banned TNT powder charge.In recent years, various countries also achieved in terms of synthesizing new high Energy Density Materials it is gratifying at
The Hexanitrohexaazaisowurtzitane (CL-20) that fruit, such as U.S. in 1989 synthesize, ρ=2.04 g/cm3, υ D=9580 m/
S, comprehensive performance is preferable, energy is higher than HMX.But the exploitation of novel high-energy density material needs a very long period,
And cost is very high, it may be said that for single chmical compound explosive exploitation to a bottleneck period, it is necessary to using other approach come
Improve the energy of explosive.
The exploitation of above compound needs a very long period, and it is at high cost, preparation process is complicated, thermal stability needs
It improves.Addition high-energy combustion agent is one of simple, effective, the direct mode for improving explosive energy.The high energy combustion studied at present
It burns agent and is concentrated mainly on Mg, Al, B and a small number of alloys.Above-mentioned metal incendiary composition makes an addition in explosive, improves to a certain extent
The quick-fried heat of explosive, explosion velocity of explosive also decreased significantly.The energy that explosive is improved using the higher hydrogen storage material of energy, is had
Important research significance and practical value.
AlH3High hydrogen content, heats of combustion, the characteristics such as nontoxic, it can be applied in high-energy fuel field.It is fired in high energy
AlH can be used in order to improve the energy characteristics of fuel in material field3To replace now widely used aluminium fuel.Through heat chemistry
Calculation shows that using AlH3Replace aluminium to can produce lower flame temperature and higher gas production, can provide than aluminium fuel more
High specific impulse.Wherein, AlH3It is combined and is formed by two kinds of strong reducing property atoms, generate H in its combustion process2, H2It can promote oxygen
Agent conflagration generates Al2O3And H2O simultaneously releases a large amount of thermal energy.Therefore, AlH3Since the combustion heat is high, good, nontoxic etc. at gas
Advantage can promise to be a kind of novel explosive high energy additive.But AlH3There is also many problems in terms of functionization:
AlH3Prepare complex and higher cost；There are still unstability for hydrogen discharging performance at low temperature；Due to AlH3It is two kinds of tools
The substance formed is combined by the atom of strong reducing property, even most stable of α-AlH3, still there is phenomena such as slowly deflation, decompose,
It is not able to satisfy the requirement of practical application.So for AlH3Structure, stability, the exploitation of synthesis and hot releasability
It is imperative to study.
Currently, China is to AlH3Research appear at greatly to its property and AlH3The conceptual phase of adduct, and really pass through
The synthetic schemes of Ji not yet proposes.For this problem, Yang Yulin et al. proposes to use diisobutyl aluminium hydride and LiBH4It is catalyzed
Agent agent control preparation α-AlH3, the available higher α-AlH of yield3, but the diisobutyl price of aluminium oxide that the method uses is inclined
Height, increases production cost, while method synthesis post-processing operation technique is cumbersome, need ether washing, dilute hydrochloric acid washing, go from
The operation such as sub- water washing, vacuum drying, is difficult to carry out large batch of industrialization production.Therefore, a kind of easy to operate, production is studied
α-three aluminum hydride preparation method at low cost, it appears particularly necessary.
Summary of the invention
To solve the deficiencies in the prior art, the purpose of the present invention is to provide one kind is mixed with lithium aluminium hydride reduction and lithium borohydride
It is catalyzed the method for preparing α-three aluminum hydride, easy to operate, easily-controlled reaction conditions.
In order to achieve the above objectives, the present invention adopts the following technical scheme that:
The method for preparing α-three aluminum hydride with lithium aluminium hydride reduction and lithium borohydride mixed catalytic, comprising the following steps: (1) mix
The preparation of catalyst；(2) synthesis of α-three aluminum hydride；(3) product purification and drying.
Further, the aforementioned method that α-three aluminum hydride is prepared with lithium aluminium hydride reduction and lithium borohydride mixed catalytic, including with
Lower step:
(1) preparation of mixed catalytic agent solution: LiAlH is weighed respectively according to quantity4And LiBH4, it is placed in a reaction flask, essence is added
Anhydrous ether after system, is sufficiently stirred, and obtains mixed catalytic agent solution, spare；
(2) synthesis of α-three aluminum hydride: the toluene after taking purification is placed in reaction vessel, and nitrogen is passed through into reaction vessel
After repeating the operation for several times, mixed catalytic agent solution obtained by step (1) is added in gas, and at reflux, stirring heating starts
The ether in catalyst is distilled out, LiAlH is slowly added dropwise at this time4With anhydrous AlCl3Mixed solution is added dropwise, it is warming up to 85~
95 DEG C of reflux, continue to distill out ether, while remaining LiAlH is added dropwise4With anhydrous AlCl3Mixed solution, the solvent distilled out return
It receives spare；It after being added dropwise, is to slowly warm up to 85~105 DEG C and flows back, cool down, until 85~95 DEG C of whens continue to flow back, slowly drop
It warms to room temperature, stands；
(3) product purification and drying: the supernatant in reaction vessel is poured out, and cleans number with the recycling design distilled out
It is secondary, until solution clarification, is finally washed again with dry toluene, be dried to obtain grizzled particle shape product after pouring out solvent.
Preferably, the aforementioned method that α-three aluminum hydride is prepared with lithium aluminium hydride reduction and lithium borohydride mixed catalytic, including it is following
Step:
(1) preparation of mixed catalytic agent solution: LiAlH is weighed respectively according to quantity4And LiBH4, it is placed in a reaction flask, essence is added
Anhydrous ether after system, is sufficiently stirred 10~50min, obtains mixed catalytic agent solution, spare；
(2) synthesis of α-three aluminum hydride: the toluene after taking 2000~3000mL to refine is placed in 10L reaction vessel, to anti-
It answers and is passed through nitrogen in container, after repeating 2~4 times, be added to mix obtained by 200~300mL step (1) as being filtered under diminished pressure mode and urge
Agent solution, at reflux, stirring heating start to distill out the ether in catalyst, it is slowly added dropwise 350 at this time~
500mLLiAlH4With anhydrous AlCl3Mixed solution controls 10~20ml/min of rate of addition, is added dropwise, is warming up to 85~95
DEG C reflux 10min, continue to distill out ether, while 3000~4500mLLiAlH of residue is added dropwise4With anhydrous AlCl3Mixed solution,
The solvent recovery distilled out is spare；After being added dropwise, it is to slowly warm up to 85~105 DEG C and the 5~20min that flows back, cooling, until 75~
Continue 20~50min of reflux at 85 DEG C, be slowly dropped to room temperature, stands；
(3) product purification and drying: the supernatant in reaction vessel is poured out, and cleans 5~9 with the recycling design distilled out
It is secondary, it until solution clarification, is finally washed 2~3 times, is poured out after solvent at 45~80 DEG C, vacuum degree is with dry toluene again
Dry 4~6h obtains grizzled particle shape product under the conditions of 320~520mmHg.
The aforementioned method that α-three aluminum hydride is prepared with lithium aluminium hydride reduction and lithium borohydride mixed catalytic, in step (1), LiAlH4
And LiBH4The volume ratio of anhydrous ether after gross mass and purification are as follows: 1.5~3g ︰, 200~300mL；LiAlH4︰ LiBH4's
Mass ratio=0.8~1.6 ︰ 0.4~1.2.
The aforementioned method that α-three aluminum hydride is prepared with lithium aluminium hydride reduction and lithium borohydride mixed catalytic, LiAlH in step (2)4
With anhydrous AlCl3Mixed solution through the following steps that prepare: take the anhydrous AlCl of 40~100g3, under the condition of ice salt bath, delay
The slow anhydrous ether being added dropwise after 180~350mL purification, is stirred after being added dropwise to AlCl3It is completely dissolved, obtains anhydrous AlCl3With
Ether mixed solution；The lithium aluminium hydride reduction of the anhydrous ether for taking 1500~3200mL to refine and 50~100g purification, after stirring 5min,
Anhydrous AlCl is slowly added dropwise while stirring3With ether mixed solution, continue 5~20min of stirring after being added dropwise, is then added
Toluene after 1500~3200mL purification stirs 3~10min, and precipitation filters, spare.
Aforementioned to be prepared in the method for α-three aluminum hydride with lithium aluminium hydride reduction and lithium borohydride mixed catalytic, step (1)~(3) are equal
It is carried out under anaerobic anhydrous condition, nitrogen is passed through before operation, drive the air in reactor away.
It is aforementioned to be prepared in the method for α-three aluminum hydride with lithium aluminium hydride reduction and lithium borohydride mixed catalytic, it further include step (4)
Solvent recovery, specifically: recovered solvent (solvent that each step recycles, including synthetic reaction in step (1)~(3)
Recycling design), be filtered with the fibrofelt (thickness about 1.5~2.2mm) that 2~4 layers of crude fibre is constituted with except dereaction mistake
Journey remains in impurity and the complete raw material of unreacted in reaction solution etc., and filtrate is placed in solvent fractionation tower, first with rectifying kettle temperature
38~42 DEG C of degree carry out the distillate that rectifying recycling rectifying still outlet temperature is 34.6~35.5 DEG C, continue rising temperature reclamation rectifying still
The distillate that outlet temperature is 110.6~111 DEG C, distillating for remaining temperature section are handled together as solvent slop；What recycling obtained
Solvent can be directly used for preparation α-three aluminum hydride without being refined.
Toluene after the anhydrous ether of heretofore described purification, the lithium aluminium hydride reduction of purification, purification is to pass through conventional side
Method carries out products therefrom after water removal purification operations to anhydrous ether, lithium aluminium hydride reduction, toluene.Also applicant can be used to apply on the same day specially
A kind of method in sharp " preparation method of α-three aluminum hydride ", refines anhydrous ether, lithium aluminium hydride reduction, toluene.
Scientific, reasonable, effective in order to ensure technical solution of the present invention, inventor has carried out a series of verification tests.Knot
Fruit is as follows.Catalyst preparation α-three aluminum hydride, preparation process operation are made using lithium aluminium hydride reduction and lithium borohydride in the present invention
Simply, production cost is low, easy to industrialized production.With use diisobutyl aluminium oxide as catalyst compared with, production cost drop
Low about 25% or so.Fig. 1 is the XRD diagram for α-three aluminum hydride being prepared using the method for the present invention.It can be seen that gained
α-three aluminum hydride crystal form is single, purity is high, and for purity up to 99.8% or more, stability is high.
The invention has the beneficial effects that: it is provided by the invention a kind of with lithium aluminium hydride reduction and the preparation of lithium borohydride mixed catalytic
The method of α-three aluminum hydride can be carried out in normal pressure and compared under low reaction temperatures, and step is simple, and easily operated, device is simple, can
To be applied to industrialized production.The method of the present invention economical and efficient, production cost is low, and gained α-three aluminum hydride crystal form is single, purity
Height, stability are high, easily stored, chemical stability be conducive to energetic material, propellant and in terms of
Using.
Detailed description of the invention
Fig. 1 is the XRD diagram of product α-three aluminum hydride of the present invention.
Specific embodiment
The present invention will be further described below in conjunction with specific embodiments.
Agents useful for same of the present invention is commercial product.
The method that embodiment 1 prepares α-three aluminum hydride with lithium aluminium hydride reduction and lithium borohydride mixed catalytic, comprising the following steps:
(1) preparation of mixed catalytic agent solution: LiAlH is weighed respectively according to quantity4And LiBH4, it is placed in a reaction flask, essence is added
Anhydrous ether after system, is sufficiently stirred 10min, obtains mixed catalytic agent solution, spare；
(2) synthesis of α-three aluminum hydride: the toluene after taking 2000mL to refine is placed in 10L reaction vessel, to reaction vessel
In be passed through nitrogen, after being repeated 2 times, mixed catalytic agent solution obtained by 300mL step (1) is added as being filtered under diminished pressure mode, return
Under stream mode, stirring heating starts to distill out the ether in catalyst, 350mLLiAlH is slowly added dropwise at this time4With anhydrous AlCl3
Mixed solution controls rate of addition 10ml/min, is added dropwise, is warming up to 85 DEG C of reflux 10min, continues to distill out ether, together
When be added dropwise residue 3000mLLiAlH4With anhydrous AlCl3Mixed solution, the solvent recovery distilled out are spare；After being added dropwise, slowly
It is warming up to 85 DEG C and the 20min that flows back, cooling is slowly dropped to room temperature, stands until 75 DEG C of whens continue the 50min that flows back；
(3) product purification and drying: the supernatant in reaction vessel is poured out, and is cleaned 5 times with the recycling design distilled out,
Until solution clarification, finally wash 2 times, poured out after solvent at 45 DEG C with dry toluene again, vacuum degree is 320mmHg condition
Lower dry 6h obtains grizzled particle shape product.Product purity is 99.8%.
LiAlH in step (2)4With anhydrous AlCl3Mixed solution through the following steps that prepare: take 100g anhydrous
AlCl3, under the condition of ice salt bath, the anhydrous ether after 350mL purification is slowly added dropwise stirs after being added dropwise to AlCl3It is completely molten
Solution, obtains anhydrous AlCl3With ether mixed solution；The lithium aluminium hydride reduction for anhydrous ether and the 100g purification for taking 3200mL to refine, is stirred
After mixing 5min, anhydrous AlCl is slowly added dropwise while stirring3With ether mixed solution, continue to stir 20min after being added dropwise, then
Toluene after 3200mL purification is added stirs 10min, and precipitation filters, spare.
Step (1)~(3) carry out under anaerobic anhydrous condition, and nitrogen is passed through before operation, drive the air in reactor away.
The method that embodiment 2 prepares α-three aluminum hydride with lithium aluminium hydride reduction and lithium borohydride mixed catalytic, comprising the following steps:
(1) preparation of mixed catalytic agent solution: LiAlH is weighed respectively according to quantity4And LiBH4, it is placed in a reaction flask, essence is added
Anhydrous ether after system, is sufficiently stirred 50min, obtains mixed catalytic agent solution, spare；
(2) synthesis of α-three aluminum hydride: the toluene after taking 3000mL to refine is placed in 10L reaction vessel, to reaction vessel
In be passed through nitrogen, after being repeated 4 times, mixed catalytic agent solution obtained by 200mL step (1) is added as being filtered under diminished pressure mode, return
Under stream mode, stirring heating starts to distill out the ether in catalyst, 500mLLiAlH is slowly added dropwise at this time4With anhydrous AlCl3
Mixed solution controls rate of addition 20ml/min, is added dropwise, is warming up to 95 DEG C of reflux 10min, continues to distill out ether, together
When be added dropwise residue 4500mLLiAlH4With anhydrous AlCl3Mixed solution, the solvent recovery distilled out are spare；After being added dropwise, slowly
It is warming up to 105 DEG C and the 5min that flows back, cooling is slowly dropped to room temperature, stands until 85 DEG C of whens continue the 20min that flows back；
(3) product purification and drying: the supernatant in reaction vessel is poured out, and is cleaned 9 times with the recycling design distilled out,
Until solution clarification, finally wash 3 times, poured out after solvent at 80 DEG C with dry toluene again, vacuum degree is 520mmHg condition
Lower dry 4h obtains grizzled particle shape product.Product purity is 99.8%.
LiAlH in step (2)4With anhydrous AlCl3Mixed solution through the following steps that prepare: take the anhydrous AlCl of 40g3,
Under the condition of ice salt bath, the anhydrous ether after 180mL purification is slowly added dropwise, is stirred after being added dropwise to AlCl3It is completely dissolved, obtains
To anhydrous AlCl3With ether mixed solution；The lithium aluminium hydride reduction for anhydrous ether and the 50g purification for taking 1500mL to refine, stirs 5min
Afterwards, anhydrous AlCl is slowly added dropwise while stirring3With ether mixed solution, continues to stir 5min after being added dropwise, then be added
Toluene after 1500mL purification stirs 3min, and precipitation filters, spare.
Step (1)~(3) carry out under anaerobic anhydrous condition, and nitrogen is passed through before operation, drive the air in reactor away.
It further include step (4) solvent recovery, specifically: recovered solvent in step (1)~(3), with 2~4 layers of crude fibre
The fibrofelt of composition is filtered, and filtrate is placed in solvent fractionation tower, first with 38~42 DEG C of progress rectifying recycling of rectifying still temperature
The distillate that rectifying still outlet temperature is 34.6~35.5 DEG C, continuing rising temperature reclamation rectifying still outlet temperature is 110.6~111 DEG C
Distillate to get.
The method that embodiment 3 prepares α-three aluminum hydride with lithium aluminium hydride reduction and lithium borohydride mixed catalytic, comprising the following steps:
(1) preparation of mixed catalytic agent solution: LiAlH is weighed respectively according to quantity4And LiBH4, it is placed in a reaction flask, essence is added
Anhydrous ether after system, is sufficiently stirred 30min, obtains mixed catalytic agent solution, spare；
(2) synthesis of α-three aluminum hydride: the toluene after taking 2500mL to refine is placed in 10L reaction vessel, to reaction vessel
In be passed through nitrogen, after being repeated 3 times, mixed catalytic agent solution obtained by 250mL step (1) is added as being filtered under diminished pressure mode, return
Under stream mode, stirring heating starts to distill out the ether in catalyst, 450mLLiAlH is slowly added dropwise at this time4With anhydrous AlCl3
Mixed solution controls rate of addition 15ml/min, is added dropwise, is warming up to 90 DEG C of reflux 10min, continues to distill out ether, together
When be added dropwise residue 3750mLLiAlH4With anhydrous AlCl3Mixed solution, the solvent recovery distilled out are spare；After being added dropwise, slowly
It is warming up to 95 DEG C and the 15min that flows back, cooling is slowly dropped to room temperature, stands until 80 DEG C of whens continue the 35min that flows back；
(3) product purification and drying: the supernatant in reaction vessel is poured out, and is cleaned 6 times with the recycling design distilled out,
Until solution clarification, finally wash 3 times, poured out after solvent at 60 DEG C with dry toluene again, vacuum degree is 400mmHg condition
Lower dry 5h obtains grizzled particle shape product.Product purity is 99.9%.
LiAlH in step (2)4With anhydrous AlCl3Mixed solution through the following steps that prepare: take the anhydrous AlCl of 70g3,
Under the condition of ice salt bath, the anhydrous ether after 250mL purification is slowly added dropwise, is stirred after being added dropwise to AlCl3It is completely dissolved, obtains
To anhydrous AlCl3With ether mixed solution；The lithium aluminium hydride reduction for anhydrous ether and the 60g purification for taking 2300mL to refine, stirs 5min
Afterwards, anhydrous AlCl is slowly added dropwise while stirring3With ether mixed solution, continues to stir 10min after being added dropwise, then be added
Toluene after 2200mL purification stirs 6min, and precipitation filters, spare.
Step (1)~(3) carry out under anaerobic anhydrous condition, and nitrogen is passed through before operation, drive the air in reactor away.
The method that embodiment 4 prepares α-three aluminum hydride with lithium aluminium hydride reduction and lithium borohydride mixed catalytic, comprising the following steps:
(1) preparation of mixed catalytic agent solution: LiAlH is weighed respectively according to quantity4And LiBH4, it is placed in a reaction flask, essence is added
Anhydrous ether after system, is sufficiently stirred 40min, obtains mixed catalytic agent solution, spare；
(2) synthesis of α-three aluminum hydride: the toluene after taking 2800mL to refine is placed in 10L reaction vessel, to reaction vessel
In be passed through nitrogen, after being repeated 4 times, mixed catalytic agent solution obtained by 240mL step (1) is added as being filtered under diminished pressure mode, return
Under stream mode, stirring heating starts to distill out the ether in catalyst, 420mLLiAlH is slowly added dropwise at this time4With anhydrous AlCl3
Mixed solution controls rate of addition 12ml/min, is added dropwise, is warming up to 88 DEG C of reflux 10min, continues to distill out ether, together
When be added dropwise residue 3300mLLiAlH4With anhydrous AlCl3Mixed solution, the solvent recovery distilled out are spare；After being added dropwise, slowly
It is warming up to 92 DEG C and the 9min that flows back, cooling is slowly dropped to room temperature, stands until 83 DEG C of whens continue the 30min that flows back；
(3) product purification and drying: the supernatant in reaction vessel is poured out, and is cleaned 7 times with the recycling design distilled out,
Until solution clarification, finally wash 2 times, poured out after solvent at 70 DEG C with dry toluene again, vacuum degree is 380mmHg condition
Lower dry 4.5h obtains grizzled particle shape product.Product purity is 99.8%.
LiAlH in step (2)4With anhydrous AlCl3Mixed solution through the following steps that prepare: take the anhydrous AlCl of 90g3,
Under the condition of ice salt bath, the anhydrous ether after 310mL purification is slowly added dropwise, is stirred after being added dropwise to AlCl3It is completely dissolved, obtains
To anhydrous AlCl3With ether mixed solution；The lithium aluminium hydride reduction for anhydrous ether and the 70g purification for taking 3000mL to refine, stirs 5min
Afterwards, anhydrous AlCl is slowly added dropwise while stirring3With ether mixed solution, continues to stir 15min after being added dropwise, then be added
Toluene after 1900mL purification stirs 8min, and precipitation filters, spare.
Step (1)~(3) carry out under anaerobic anhydrous condition, and nitrogen is passed through before operation, drive the air in reactor away.
The method that embodiment 5 prepares α-three aluminum hydride with lithium aluminium hydride reduction and lithium borohydride mixed catalytic, comprising the following steps:
(1) preparation of mixed catalytic agent solution: LiAlH is weighed respectively according to quantity4And LiBH4, it is placed in a reaction flask, essence is added
Anhydrous ether after system, is sufficiently stirred 20min, obtains mixed catalytic agent solution, spare；
(2) synthesis of α-three aluminum hydride: the toluene after taking 2300mL to refine is placed in 10L reaction vessel, to reaction vessel
In be passed through nitrogen, after being repeated 2 times, mixed catalytic agent solution obtained by 270mL step (1) is added as being filtered under diminished pressure mode, return
Under stream mode, stirring heating starts to distill out the ether in catalyst, 380mLLiAlH is slowly added dropwise at this time4With anhydrous AlCl3
Mixed solution controls rate of addition 18ml/min, is added dropwise, is warming up to 93 DEG C of reflux 10min, continues to distill out ether, together
When be added dropwise residue 4300mLLiAlH4With anhydrous AlCl3Mixed solution, the solvent recovery distilled out are spare；After being added dropwise, slowly
It is warming up to 100 DEG C and the 16min that flows back, cooling is slowly dropped to room temperature, stands until 78 DEG C of whens continue the 40min that flows back；
(3) product purification and drying: the supernatant in reaction vessel is poured out, and is cleaned 8 times with the recycling design distilled out,
Until solution clarification, finally wash 3 times, poured out after solvent at 50 DEG C with dry toluene again, vacuum degree is 500mmHg condition
Lower dry 5.5h obtains grizzled particle shape product.Product purity is 99.9%.
LiAlH in step (2)4With anhydrous AlCl3Mixed solution through the following steps that prepare: take the anhydrous AlCl of 60g3,
Under the condition of ice salt bath, the anhydrous ether after 200mL purification is slowly added dropwise, is stirred after being added dropwise to AlCl3It is completely dissolved, obtains
To anhydrous AlCl3With ether mixed solution；The lithium aluminium hydride reduction for anhydrous ether and the 80g purification for taking 1800mL to refine, stirs 5min
Afterwards, anhydrous AlCl is slowly added dropwise while stirring3With ether mixed solution, continues to stir 12min after being added dropwise, then be added
Toluene after 2800mL purification stirs 5min, and precipitation filters, spare.
Step (1)~(3) carry out under anaerobic anhydrous condition, and nitrogen is passed through before operation, drive the air in reactor away.
It further include step (4) solvent recovery, specifically: recovered solvent in step (1)~(3), with 2~4 layers of crude fibre
The fibrofelt of composition is filtered, and filtrate is placed in solvent fractionation tower, first with 38~42 DEG C of progress rectifying recycling of rectifying still temperature
The distillate that rectifying still outlet temperature is 34.6~35.5 DEG C, continuing rising temperature reclamation rectifying still outlet temperature is 110.6~111 DEG C
Distillate to get.
Claims (5)
1. the method for preparing α-three aluminum hydride with lithium aluminium hydride reduction and lithium borohydride mixed catalytic, it is characterised in that: including following step
It is rapid:
(1) preparation of mixed catalytic agent solution: LiAlH is weighed respectively according to quantity4And LiBH4, it is placed in a reaction flask, after purification is added
Anhydrous ether, 10~50min is sufficiently stirred, obtains mixed catalytic agent solution, it is spare；
(2) synthesis of α-three aluminum hydride: the toluene after taking 2000~3000mL to refine is placed in 10L reaction vessel, is held to reaction
It is passed through nitrogen in device, after repeating 2~4 times, mixed catalyst obtained by 200~300mL step (1) is added as being filtered under diminished pressure mode
Solution, at reflux, stirring heating start to distill out the ether in catalyst, it is slowly added dropwise 350 at this time~
500mLLiAlH4With anhydrous AlCl3Mixed solution controls 10~20ml/min of rate of addition, is added dropwise, is warming up to 85~95
DEG C reflux 10min, continue to distill out ether, while 3000~4500mLLiAlH of residue is added dropwise4With anhydrous AlCl3Mixed solution,
The solvent recovery distilled out is spare；After being added dropwise, it is to slowly warm up to 85~105 DEG C and the 5~20min that flows back, cooling, until 75~
Continue 20~50min of reflux at 85 DEG C, be slowly dropped to room temperature, stands；
(3) product purification and drying: the supernatant in reaction vessel is poured out, and is cleaned 5~9 times with the recycling design distilled out,
It until solution clarification, is finally washed 2~3 times, is poured out after solvent at 45~80 DEG C, vacuum degree 320 with dry toluene again
Dry 4~6h obtains grizzled particle shape product under the conditions of~520mmHg.
2. the method according to claim 1 that α-three aluminum hydride is prepared with lithium aluminium hydride reduction and lithium borohydride mixed catalytic,
It is characterized in that: in the step (1), LiAlH4And LiBH4The volume ratio of anhydrous ether after gross mass and purification are as follows: 1.5~
200~300mL of 3g ︰；LiAlH4︰ LiBH4Mass ratio=0.8~1.6 ︰ 0.4~1.2.
3. the method according to claim 1 that α-three aluminum hydride is prepared with lithium aluminium hydride reduction and lithium borohydride mixed catalytic,
It is characterized in that: LiAlH in the step (2)4With anhydrous AlCl3Mixed solution through the following steps that prepare: take 40~100g
Anhydrous AlCl3, under the condition of ice salt bath, be slowly added dropwise 180~350mL purification after anhydrous ether, stirred after being added dropwise to
AlCl3It is completely dissolved, obtains anhydrous AlCl3With ether mixed solution；Take 1500~3200mL refine anhydrous ether and 50~
Anhydrous AlCl is slowly added dropwise after stirring 5min in the lithium aluminium hydride reduction of 100g purification while stirring3With ether mixed solution, drip
Continuing 5~20min of stirring after finishing, the toluene after 1500~3200mL purification is then added stirs 3~10min, and precipitation filters,
It is spare.
4. the method according to claim 1 that α-three aluminum hydride is prepared with lithium aluminium hydride reduction and lithium borohydride mixed catalytic,
Be characterized in that: step (1)~(3) carry out under anaerobic anhydrous condition, and nitrogen is passed through before operation, drive the sky in reactor away
Gas.
5. the method according to claim 1 that α-three aluminum hydride is prepared with lithium aluminium hydride reduction and lithium borohydride mixed catalytic,
It is characterized in that: further including step (4) solvent recovery, specifically: recovered solvent in step (1)~(3), with 2~4 layers of crude fibre
The fibrofelt of composition is filtered, and filtrate is placed in solvent fractionation tower, first with 38~42 DEG C of progress rectifying recycling of rectifying still temperature
The distillate that rectifying still outlet temperature is 34.6~35.5 DEG C, continuing rising temperature reclamation rectifying still outlet temperature is 110.6~111 DEG C
Distillate to get.
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