CN105197891A - Method for extracting alpha-AlH3 powder from nano AlH3/metal chlorides - Google Patents
Method for extracting alpha-AlH3 powder from nano AlH3/metal chlorides Download PDFInfo
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- CN105197891A CN105197891A CN201510654627.3A CN201510654627A CN105197891A CN 105197891 A CN105197891 A CN 105197891A CN 201510654627 A CN201510654627 A CN 201510654627A CN 105197891 A CN105197891 A CN 105197891A
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- alh
- powder
- diethyl ether
- etherate
- ether solution
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- 239000000843 powder Substances 0.000 title claims abstract description 160
- 238000000034 method Methods 0.000 title claims abstract description 46
- 229910001510 metal chloride Inorganic materials 0.000 title claims abstract description 40
- 229910000091 aluminium hydride Inorganic materials 0.000 title abstract 13
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 title abstract 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 196
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000007791 liquid phase Substances 0.000 claims abstract description 33
- 239000007790 solid phase Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000004140 cleaning Methods 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 20
- 229910010082 LiAlH Inorganic materials 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 125000001033 ether group Chemical group 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- 238000010671 solid-state reaction Methods 0.000 description 3
- 239000011232 storage material Substances 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004449 solid propellant Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 101100323029 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) alc-1 gene Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- -1 aluminium alkane Chemical class 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses a method for extracting alpha-AlH3 powder from nano AlH3/metal chlorides, which relates to a method for preparing alpha-AlH3 powder. The invention aims to solve the problem that existing methods for preparing alpha-AlH3 powder are high in cost, low in reaction yield, high in equipment requirement and large in risk, and pollute the environment. The method comprises the following steps: 1, preparing an ethyl ether solution of solid-phase metal salts and liquid-phase AlH3 etherate; 2, preparing an ethyl ether solution of liquid-phase AlH3 etherate; 3, preparing off-white powder; and 4, adding the off-white powder into a hydrochloric acid solution, cleaning the obtained object by using distilled water and absolute ethyl alcohol, and drying the obtained product, so that alpha-AlH3 powder is obtained. The particle size of the alpha-AlH3 powder prepared according to the invention can reach about 20-30 mu m, and the decomposition temperature of the alpha-AlH3 powder cleaned by using the hydrochloric acid solution can reach about 184 DEG C, and therefore, the alpha-AlH3 powder is good in stability. The method disclosed by the invention is suitable for preparing alpha-AlH3 powder.
Description
Technical field
The present invention relates to one and prepare α-AlH
3the method of powder.
Technical background
AlH
3also known as aluminium alkane, be beige crystals, AlH
3hydrogeneous mass density be 10.1wt%, its hydrogen-storage amount, apparently higher than the target reaching 5.5wt% for 2015 of USDOE defined, is high-performance hydrogen storage material, also can be applied in propelling agent as special energy storage material.Use AlH
3substitute for Al, as propelling agent, at least can improve solid-propellant mass specific impulse 100NSkg
-1, and AlH
3the H of himself weight 10% is discharged in decomposition course
2, reducing the molecular-weight average of combustion gas, is replace Al as the major cause of solid propellant with it.Find AlH after deliberation
3have six kinds of crystal formations, wherein most suitable as hydrogen storage material and propelling agent is exactly α-AlH
3.
At present, AlH
3preparation method be main mainly with Moist chemical synthesis: namely with excessive LiAlH
4deng basic metal complex hydride and AlCl
3for initial reactant, containing LiBH
4diethyl ether solution in reaction, filter, turn brilliant, can AlH be obtained
3(reaction formula 1).But, the raw material Li AlH that this method is not only used
4expensive, reaction yield is low, and AlH
3leaching process need anhydrous and oxygen-free to operate, it is high to equipment requirements, and operating process high risk is large, so method is only applicable to prepare AlH in laboratory
3sample; After this, the people such as Mark proposes with AlC1
3and LiAlH
4for raw material solid phase synthesis AlH
3/ LiCl nano-complex, and adopt Nitromethane 99Min. to be the method for solvent extraction by product LiCl (reaction formula 2).But there is following shortcoming in the method: 1) reaction raw materials is not improved, LiAlH
4expensive; 2) this solid state reaction generate four kinds of different crystal formation α-, α '-, β-, γ-AlH
3, make subsequent extracted complex procedures, extraction cost is high, efficiency is low.
Existing preparation AlH
3processing method, ubiquity preparation process very complicated, efficiency are low, starting material and the shortcoming such as process costs is high, big for environment pollution.In order to explore AlH
3low cost green manufacturing approach, the present patent application person proposes one and prepares AlH
3the novel method of material: first prepare nanometer AlH
3/ metal chloride, and then utilize solvent method by LiCl, MgCl
2remove and obtain AlH
3pressed powder.The method there are easy and simple to handle, starting material and process costs low, the advantages such as efficiency is high, environmentally friendly.
Summary of the invention
The object of the invention is to solve existing preparation α-AlH
3it is high to there is cost in the method for powder, and reaction yield is low, high to equipment requirements, dangerous large, the problem of contaminate environment, and provides a kind of from nanometer AlH
3α-AlH is extracted in/metal chloride
3the method of powder.
A kind of from nanometer AlH
3α-AlH is extracted in/metal chloride
3the method of powder, completes according to the following steps:
One, by nanometer AlH
3/ metal chloride joins in solvent, then low whipping speed is stir 10min ~ 90min under 60r/min ~ 100r/min, obtains the metal-salt of solid phase and the AlH of liquid phase
3the diethyl ether solution of etherate;
Nanometer AlH described in step one
3/ metal chloride is AlH
3/ MgCl
2nano-complex powder or AlH
3/ LiCl nano-complex powder;
Nanometer AlH described in step one
3the quality of/metal chloride and the volume ratio of solvent are (1g ~ 3g): 50mL;
Two, by the metal-salt of solid phase and the AlH of liquid phase
3diethyl ether solution centrifugation 10min ~ 30min under centrifugal speed is 3000r/min ~ 12000r/min of etherate, removes the metal-salt of solid phase, obtains the AlH of liquid phase
3the diethyl ether solution of etherate;
Three, under anhydrous and oxygen-free condition, the AlH of liquid phase that cold-trap will obtain in step 2 is used
3ether in the diethyl ether solution of etherate is drained, and obtains AlH
3etherate; By AlH
3etherate vacuum tightness be 40Pa ~ 50Pa, turn a brilliant temperature be 50 DEG C ~ 120 DEG C at turn brilliant 2h ~ 12h, obtain canescence powder;
Four, canescence powder is joined in hydrochloric acid soln, then low whipping speed is stirring reaction 5min ~ 30min under 20r/min ~ 40r/min, obtains the canescence powder after hydrochloric acid cleaning; Use distilled water and dehydrated alcohol to clean 3 times ~ 5 times to the canescence powder after hydrochloric acid cleaning respectively successively, then at temperature is 60 DEG C ~ 90 DEG C dry 3h ~ 5h, obtain α-AlH
3powder;
The massfraction of the hydrochloric acid soln described in step 4 is 1% ~ 10%;
The quality of canescence powder described in step 4 and the volume ratio 5g:50mL of hydrochloric acid soln;
α-AlH described in step 4
3the particle diameter of powder is 20 μm ~ 30 μm.
Advantage of the present invention:
One, based on nanometer AlH
3have in organic solvents such as being more soluble in ether, form the advantages such as etherate, adopt separation method of the present invention easier from nanometer AlH
3α-AlH is extracted in/metal chloride
3powder; Therefore, extracting method of the present invention is generally applicable to all nanometer AlH
3the extraction process of/metal chloride;
Two, the present invention adopts centrifugation and liquid phase to extract the method combined to prepare α-AlH
3powder, the method has the advantages such as simple process, cost is low, environmental pollution is little; And prepare α-AlH as one
3the new way of powder, the present invention successfully solves solid phase synthesis AlH
3α-AlH in process
3an extraction difficult problem for powder;
Three, the present invention is by extracting the α-AlH obtained
3powder has the advantages such as powder granularity is large, smooth surface, good stability; And α-AlH
3the granular size of powder can reach 20 μm ~ about 30 μm, and the α-AlH after hydrochloric acid soln washing
3powder de-agglomeration temperature can reach about 184 DEG C, good stability.
The present invention is applicable to preparation α-AlH
3powder.
Accompanying drawing explanation
Fig. 1 is XRD figure spectrum, and in Fig. 1,1 is γ-AlH
3standard x RD curve, 2 is MgCl
2standard x RD curve, 3 is the AlH that 2. embodiment one step one obtains
3/ MgCl
2the XRD curve of nano-complex powder, 4 is the AlH that embodiment one step 3 obtains
3the XRD curve of etherate, ● be MgCl
2; ▲ be γ-AlH
3; △ is AlH
3et
2o;
Fig. 2 is the XRD figure spectrum of the canescence powder that embodiment one step 3 obtains, and in Fig. 2,1 is MgCl
2standard x RD curve, 2 is γ-AlH
3standard x RD curve, 3 is α-AlH
3standard x RD curve, 4 is the XRD curve of the canescence powder that embodiment one step 3 obtains, ● be MgCl
2; ▲ be γ-AlH
3; △ is α-AlH
3;
Fig. 3 is the α-AlH that embodiment one step 5 obtains
3the XRD figure spectrum of powder, in Fig. 3,1 is the standard x RD curve of Al, and 2 is α-AlH
3standard x RD curve, 3 is the α-AlH that embodiment one step 4 obtains
3the XRD curve of powder, ▼ is Al; △ is α-AlH
3;
Fig. 4 is the AlH that 2. embodiment one step one obtains
3/ MgCl
2the SEM figure of nano-complex powder;
Fig. 5 is the SEM figure of the canescence powder that embodiment one step 3 obtains;
Fig. 6 is the α-AlH that embodiment one step 4 obtains
3the SEM figure of powder;
Fig. 7 is the α-AlH that embodiment one step 4 obtains
3the TG curve of powder;
Fig. 8 is the α-AlH that embodiment one step 4 obtains
3the DSC curve of powder.
Embodiment
Embodiment one: present embodiment is a kind of from nanometer AlH
3α-AlH is extracted in/metal chloride
3the method of powder completes according to the following steps:
One, by nanometer AlH
3/ metal chloride joins in solvent, then low whipping speed is stir 10min ~ 90min under 60r/min ~ 100r/min, obtains the metal-salt of solid phase and the AlH of liquid phase
3the diethyl ether solution of etherate;
Nanometer AlH described in step one
3/ metal chloride is AlH
3/ MgCl
2nano-complex powder or AlH
3/ LiCl nano-complex powder;
Nanometer AlH described in step one
3the quality of/metal chloride and the volume ratio of solvent are (1g ~ 3g): 50mL;
Two, by the metal-salt of solid phase and the AlH of liquid phase
3diethyl ether solution centrifugation 10min ~ 30min under centrifugal speed is 3000r/min ~ 12000r/min of etherate, removes the metal-salt of solid phase, obtains the AlH of liquid phase
3the diethyl ether solution of etherate;
Three, under anhydrous and oxygen-free condition, the AlH of liquid phase that cold-trap will obtain in step 2 is used
3ether in the diethyl ether solution of etherate is drained, and obtains AlH
3etherate; By AlH
3etherate vacuum tightness be 40Pa ~ 50Pa, turn a brilliant temperature be 50 DEG C ~ 120 DEG C at turn brilliant 2h ~ 12h, obtain canescence powder;
Four, canescence powder is joined in hydrochloric acid soln, then low whipping speed is stirring reaction 5min ~ 30min under 20r/min ~ 40r/min, obtains the canescence powder after hydrochloric acid cleaning; Use distilled water and dehydrated alcohol to clean 3 times ~ 5 times to the canescence powder after hydrochloric acid cleaning respectively successively, then at temperature is 60 DEG C ~ 90 DEG C dry 3h ~ 5h, obtain α-AlH
3powder;
The massfraction of the hydrochloric acid soln described in step 4 is 1% ~ 10%;
The quality of canescence powder described in step 4 and the volume ratio 5g:50mL of hydrochloric acid soln;
α-AlH described in step 4
3the particle diameter of powder is 20 μm ~ 30 μm.
The advantage of present embodiment:
One, based on nanometer AlH
3have in organic solvents such as being more soluble in ether, form the advantages such as etherate, adopt the separation method of present embodiment easier from nanometer AlH
3α-AlH is extracted in/metal chloride
3powder; Therefore, the extracting method that present embodiment adopts generally is applicable to all nanometer AlH
3the extraction process of/metal chloride;
Two, present embodiment adopts centrifugation to extract with liquid phase the method combined and prepare α-AlH
3powder, the method has the advantages such as simple process, cost is low, environmental pollution is little; And prepare α-AlH as one
3the new way of powder, present embodiment successfully solves solid phase synthesis AlH
3α-AlH in process
3an extraction difficult problem for powder;
Three, present embodiment is by extracting the α-AlH obtained
3powder has the advantages such as powder granularity is large, smooth surface, good stability; And α-AlH
3the granular size of powder can reach 20 μm ~ about 30 μm, and the α-AlH after hydrochloric acid soln washing
3powder de-agglomeration temperature can reach about 184 DEG C, good stability.
Present embodiment is applicable to preparation α-AlH
3powder.
Embodiment two: present embodiment and embodiment one difference are: the AlH described in step one
3/ MgCl
2nano-complex powder is prepared according to the following steps:
The magnesium alloy powder of 1., to be the magnesium dust of 0.1mm ~ 2mm or granularity by granularity be 0.1mm ~ 2mm is placed in ball grinder, be (30 ~ 120) in ball material mass ratio: the ratio of 1 puts into abrading-ball, in a hydrogen atmosphere with the speed ball milling 15h ~ 20h of 250r/min ~ 400r/min, obtain the nanocrystalline M gH that grain-size is 9nm ~ 11nm, powder size is 1 μm ~ 10 μm
2powder;
Step 1. described in magnesium alloy be ZK60; In described ZK60, Mg content is 93.5%, Zn content be 6%, Zr content is 0.5%;
2., ball milling, reaction: be first 9nm ~ 11nm by grain-size, powder size is the nanocrystalline M gH of 1 μm ~ 10 μm
2powder and AlCl
3powder mixes, and is then placed in ball grinder, is (30 ~ 120): the ratio of 1 puts into abrading-ball in ball material mass ratio; Again under hydrogen atmosphere and pressure are the condition of 0.2MPa ~ 1.0MPa, carry out ball milling with the speed of 250r/min ~ 400r/min, Ball-milling Time 15 ~ 30h, obtains AlH
3/ MgCl
2nano-complex powder;
Step 2. described in grain-size be 9nm ~ 11nm, powder size is the nanocrystalline M gH of 1 μm ~ 10 μm
2the amount of substance of powder and AlCl
3the amount of substance of powder is than being (2.7 ~ 3.2): 2.Other steps are identical with embodiment one.
Embodiment three: one of present embodiment and embodiment one or two difference is: the AlH described in step one
3/ LiCl nano-complex powder is prepared according to the following steps:
1., LiAlH is taken
4, AlCl
3and LiBH
4;
Step 1. described in LiAlH
4with AlCl
3mol ratio be (2.8 ~ 3.2): 1;
Step 1. described in LiBH
4with AlCl
3mol ratio be (2 ~ 10): 1;
2., by step 1. in the LiAlH that takes
4, AlCl
3and LiBH
4be dissolved into respectively in three parts of ether, obtain LiAlH
4diethyl ether solution, AlCl
3diethyl ether solution and LiBH
4diethyl ether solution;
Step 2. described in LiAlH
4liAlH in diethyl ether solution
4be 1:(20 ~ 50 with the mol ratio of ether);
Step 2. described in AlCl
3alCl in diethyl ether solution
3be 1:(20 ~ 50 with the mol ratio of ether);
Step 2. described in LiBH
4liBH in diethyl ether solution
4be 1:(20 ~ 50 with the mol ratio of ether);
3. the LiAlH, 2. step obtained
4diethyl ether solution, AlCl
3diethyl ether solution and LiBH
4diethyl ether solution mixes, then low whipping speed is stir 10min ~ 20min under 250r/min ~ 400r/min, obtains mixing solutions; Mixing solutions is heated to 35 DEG C ~ 45 DEG C, then reacts 20min ~ 60min at temperature is 35 DEG C ~ 45 DEG C, then carry out underpressure distillation, remove ether, obtain AlH
3/ LiCl nano-complex powder;
Step 3. described in LiAlH
4diethyl ether solution, AlCl
3diethyl ether solution and LiBH
4the volume ratio of diethyl ether solution is 1:1:1.Other steps are identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three difference is: the solvent described in step one is ether or ether/toluene mixture liquid; Described ether/toluene mixture liquid is mixed by ether and toluene, and the volume ratio of ether and toluene is (1 ~ 5): 1.Other steps are identical with embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four difference is: by nanometer AlH in step one
3/ metal chloride joins in solvent, then low whipping speed is stir 10min ~ 30min under 60r/min ~ 80r/min, obtains the metal-salt of solid phase and the AlH of liquid phase
3the diethyl ether solution of etherate.Other steps are identical with embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five difference is: by nanometer AlH in step one
3/ metal chloride joins in solvent, then low whipping speed is stir 30min ~ 90min under 80r/min ~ 100r/min, obtains the metal-salt of solid phase and the AlH of liquid phase
3the diethyl ether solution of etherate.Other steps are identical with embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six difference is: in step 3 under anhydrous and oxygen-free condition, uses the AlH of liquid phase that cold-trap will obtain in step 2
3ether in the diethyl ether solution of etherate is drained, and obtains AlH
3etherate; By AlH
3etherate vacuum tightness be 40Pa ~ 50Pa, turn a brilliant temperature be 50 DEG C ~ 90 DEG C at turn brilliant 2h ~ 8h, obtain canescence powder.Other steps are identical with embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven difference is: in step 3 under anhydrous and oxygen-free condition, uses the AlH of liquid phase that cold-trap will obtain in step 2
3ether in the diethyl ether solution of etherate is drained, and obtains AlH
3etherate; By AlH
3etherate vacuum tightness be 40Pa ~ 50Pa, turn a brilliant temperature be 90 DEG C ~ 120 DEG C at turn brilliant 8h ~ 12h, obtain canescence powder.Other steps are identical with embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight difference is: the massfraction of the hydrochloric acid soln described in step 4 is 1% ~ 5%.Other steps are identical with embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to nine difference is: the massfraction of the hydrochloric acid soln described in step 4 is 5% ~ 10%.Other steps are identical with embodiment one to nine.
Embodiment 11: one of present embodiment and embodiment one to ten difference is: the nanometer AlH described in step one
3the quality of/metal chloride and the volume ratio of solvent are 1g:50mL.Other steps are identical with embodiment one to ten.
Embodiment 12: one of present embodiment and embodiment one to ten one difference is: by the metal-salt of solid phase and the AlH of liquid phase in step 2
3diethyl ether solution centrifugation 10min under centrifugal speed is 3000r/min of etherate, removes the metal-salt of solid phase, obtains the AlH of liquid phase
3the diethyl ether solution of etherate.Other steps are identical with embodiment one to ten one.
Embodiment 13: one of present embodiment and embodiment one to ten two difference is: in step 3 under anhydrous and oxygen-free condition, uses the AlH of liquid phase that cold-trap will obtain in step 2
3ether in the diethyl ether solution of etherate is drained, and obtains AlH
3etherate; By AlH
3etherate vacuum tightness be 40Pa, turn a brilliant temperature be 60 DEG C at turn brilliant 2h, obtain canescence powder.Other steps are identical with embodiment one to ten two.
Embodiment 14: one of present embodiment and embodiment one to ten three difference is: join in hydrochloric acid soln by canescence powder in step 4, low whipping speed is stirring reaction 10min under 20r/min again, obtains the canescence powder after hydrochloric acid cleaning; Use distilled water and dehydrated alcohol to clean 4 times to the canescence powder after hydrochloric acid cleaning respectively successively, then at temperature is 60 DEG C dry 3h, obtain α-AlH
3powder.Other steps are identical with embodiment one to ten three.
Embodiment 15: one of present embodiment and embodiment one to ten four difference is: the massfraction of the hydrochloric acid soln described in step 4 is 5%.Other steps are identical with embodiment one to ten four.
Embodiment 16: one of present embodiment and embodiment one to ten five difference is: the quality of canescence powder described in step 4 and the volume ratio 5g:50mL of hydrochloric acid soln.Other steps are identical with embodiment one to ten five.
Following examples are adopted to verify beneficial effect of the present invention:
Embodiment one: a kind of from nanometer AlH
3α-AlH is extracted in/metal chloride
3the method of powder completes according to the following steps:
One, by nanometer AlH
3/ metal chloride joins in solvent, then low whipping speed is stir 10min under 60r/min, obtains the metal-salt of solid phase and the AlH of liquid phase
3the diethyl ether solution of etherate;
Solvent described in step one is ether;
Nanometer AlH described in step one
3the quality of/metal chloride and the volume ratio of solvent are 1g:50mL;
Nanometer AlH described in step one
3/ metal chloride is AlH
3/ MgCl
2nano-complex powder, preparation method is as follows;
1. be, that the magnesium dust of 0.1mm ~ 2mm is placed in ball grinder by granularity, the ratio being 90:1 in ball material mass ratio puts into abrading-ball, in a hydrogen atmosphere with the speed ball milling 15h of 300r/min, obtain the nanocrystalline M gH that grain-size is 9nm ~ 11nm, powder size is 1 μm ~ 10 μm
2powder;
2., ball milling, reaction: be first 9nm ~ 11nm by grain-size, powder size is the nanocrystalline M gH of 1 μm ~ 10 μm
2powder and AlCl
3powder mixes, and is then placed in ball grinder, and the ratio being 30:1 in ball material mass ratio puts into abrading-ball; Again under hydrogen atmosphere and pressure are the condition of 0.2MPa, carry out ball milling with the speed of 250r/min, Ball-milling Time 15h, obtains AlH
3/ MgCl
2nano-complex powder;
Step 2. described in grain-size be 9nm ~ 11nm, powder size is the nanocrystalline M gH of 1 μm ~ 10 μm
2the amount of substance of powder and AlCl
3the amount of substance of powder is than being 3:2;
Two, by the metal-salt of solid phase and the AlH of liquid phase
3diethyl ether solution centrifugation 10min under centrifugal speed is 3000r/min of etherate, removes the metal-salt of solid phase, obtains the AlH of liquid phase
3the diethyl ether solution of etherate;
Three, under anhydrous and oxygen-free condition, the AlH of liquid phase that cold-trap will obtain in step 2 is used
3ether in the diethyl ether solution of etherate is drained, and obtains AlH
3etherate; By AlH
3etherate vacuum tightness be 40Pa, turn a brilliant temperature be 60 DEG C at turn brilliant 2h, obtain canescence powder;
Four, canescence powder is joined in hydrochloric acid soln, then low whipping speed is stirring reaction 10min under 20r/min, obtains the canescence powder after hydrochloric acid cleaning; Use distilled water and dehydrated alcohol to clean 4 times to the canescence powder after hydrochloric acid cleaning successively, then at temperature is 60 DEG C dry 3h, obtain α-AlH
3powder;
The massfraction of the hydrochloric acid soln described in step 4 is 5%;
The quality of canescence powder described in step 4 and the volume ratio 5g:50mL of hydrochloric acid soln;
α-AlH described in step 4
3the particle diameter of powder is 20 μm ~ 30 μm.
Fig. 1 is XRD figure spectrum, and in Fig. 1,1 is γ-AlH
3standard x RD curve, 2 is MgCl
2standard x RD curve, 3 is the AlH that 2. embodiment one step one obtains
3/ MgCl
2the XRD curve of nano-complex powder, 4 is the AlH that embodiment one step 3 obtains
3the XRD curve of etherate, ● be MgCl
2; ▲ be γ-AlH
3; △ is AlH
3et
2o;
As can be seen from Figure 1 at MgH
2powder and AlCl
3alH at the end of powder mechanical ball milling solid state reaction
3be converted into nanocrystalline, and can be calculated by XRD grain-size, AlH
3the average grain size of phase can reach 6.5nm; By the AlH of liquid phase
3ether in the diethyl ether solution of etherate steams, the AlH obtained
3etherate is AlH
3nEt
2o white solid, AlH
3nEt
2in O, the span of n is 0.5≤n≤3; Because magnesium chloride crystal grain is less, do not remove completely by flash liberation.So, AlH
3containing a small amount of MgCl in etherate
2solid.
Fig. 2 is the XRD figure spectrum of the canescence powder that embodiment one step 3 obtains, and in Fig. 2,1 is MgCl
2standard x RD curve, 2 is γ-AlH
3standard x RD curve, 3 is α-AlH
3standard x RD curve, 4 is the XRD curve of the canescence powder that embodiment one step 3 obtains, ● be MgCl
2; ▲ be γ-AlH
3; △ is α-AlH
3;
As can be seen from Figure 2, for making chemical formula AlH
3nEt
2the AlH of O
3etherate (AlH
3nEt
2in O, the span of n is 0.5≤n≤3) change α-AlH into
3, by the AlH obtained
3etherate is 60 DEG C of vacuum-dryings.Turn brilliant through 60 DEG C, can obtain containing γ-AlH
3with α-AlH
3the powder of phase.
Fig. 3 is the α-AlH that embodiment one step 5 obtains
3the XRD figure spectrum of powder, in Fig. 3,1 is the standard x RD curve of Al, and 2 is α-AlH
3standard x RD curve, 3 is the α-AlH that embodiment one step 4 obtains
3the XRD curve of powder, ▼ is Al; △ is α-AlH
3;
As can be seen from Figure 3 through hydrochloric acid soln washing canescence powder (canescence powder is α/γ-AlH
3powder) after XRD figure can find out the by product MgCl that solid state reaction produces
2can remove completely after hydrochloric acid soln washing; In addition, find in figure 3 in product containing a small amount of Al phase; This is due in hydrochloric acid soln washing process, residual γ-AlH in product
3occur with the α phase of sub-fraction instability that decomposition reaction causes.
Fig. 4 is the AlH that 2. embodiment one step one obtains
3/ MgCl
2the SEM figure of nano-complex powder;
AlH as can be seen from Figure 4
3/ MgCl
2nano-complex powder defines AlH after adding ether
3etherate (AlH
3etherate is AlH
3nEt
2o, AlH
3nEt
2in O, the span of n is 0.5≤n≤3), with the AlH be evenly distributed
3nano-complex is compared, AlH
3etherate presents irregular spherical morphology.In addition, AlH can also be observed significantly from Fig. 4
3etherate particle is increased to about 3-5 μm.
Fig. 5 is the SEM figure of the canescence powder that embodiment one step 3 obtains;
As can be seen from Figure 5 after 60 DEG C of heating turn crystalline substance, and add LiBH
4the Traditional liquid phase synthesis of additive is compared, the product α-AlH in this figure
3smooth surface, its granularity can reach about 20 μm; But from surface observation to a small amount of MgCl
2be attached to α-AlH
3on the surface, its granularity is compared large about about 1 μm in α phase.
Fig. 6 is the α-AlH that embodiment one step 4 obtains
3the SEM figure of powder;
(white powder is γ/α-AlH to canescence powder as can be seen from Figure 6
3) after hydrochloric acid soln washing, although exist without any muriate in product, α phase surface pattern has very large change.Major cause is: the α-AlH of γ phase and part instability
3caused by decomposing; From Fig. 6, can be observed the particle of spherical shape, this particle is Al phase.
Fig. 7 is the α-AlH that embodiment one step 4 obtains
3the TG curve of powder; The test condition of Fig. 7 is at N
2under protection, be warming up to 280 DEG C with the temperature rise rate of 10 DEG C/min from 40 DEG C;
As can be seen from Figure 7, the α-AlH that obtains of embodiment one step 4
3the weight loss of powder between 40 DEG C ~ 240 DEG C can reach 9.73wt%, this result and AlH
3theoretical hydrogen desorption capacity (10.1wt%) consistent.
Use the α-AlH that TG-DSC instrument obtains embodiment one step 4
3powder is tested, and test condition is N
2purge, purging speed is 5mL/min, is warming up to 280 DEG C with the temperature rise rate of 10 DEG C/min from 40 DEG C; As shown in Figure 8;
Fig. 8 is the α-AlH that embodiment one step 4 obtains
3the DSC curve of powder;
As can be seen from Figure 8, there is a remarkable endotherm(ic)peak at about 180 DEG C in curve, this absorption peak is due to α-AlH
3powder generation decomposition reaction produces; This illustrates α-AlH after hydrochloric acid soln cleaning
3decomposition temperature is 184 DEG C, and the product after this result shows hydrochloric acid soln cleaning has good thermostability.
Claims (10)
1. one kind from nanometer AlH
3α-AlH is extracted in/metal chloride
3the method of powder, is characterized in that a kind of from nanometer AlH
3α-AlH is extracted in/metal chloride
3the method of powder completes according to the following steps:
One, by nanometer AlH
3/ metal chloride joins in solvent, then low whipping speed is stir 10min ~ 90min under 60r/min ~ 100r/min, obtains the metal-salt of solid phase and the AlH of liquid phase
3the diethyl ether solution of etherate;
Nanometer AlH described in step one
3/ metal chloride is AlH
3/ MgCl
2nano-complex powder or AlH
3/ LiCl nano-complex powder;
Nanometer AlH described in step one
3the quality of/metal chloride and the volume ratio of solvent are (1g ~ 3g): 50mL;
Two, by the metal-salt of solid phase and the AlH of liquid phase
3diethyl ether solution centrifugation 10min ~ 30min under centrifugal speed is 3000r/min ~ 12000r/min of etherate, removes the metal-salt of solid phase, obtains the AlH of liquid phase
3the diethyl ether solution of etherate;
Three, under anhydrous and oxygen-free condition, the AlH of liquid phase that cold-trap will obtain in step 2 is used
3ether in the diethyl ether solution of etherate is drained, and obtains AlH
3etherate; By AlH
3etherate vacuum tightness be 40Pa ~ 50Pa, turn a brilliant temperature be 50 DEG C ~ 120 DEG C at turn brilliant 2h ~ 12h, obtain canescence powder;
Four, canescence powder is joined in hydrochloric acid soln, then low whipping speed is stirring reaction 5min ~ 30min under 20r/min ~ 40r/min, obtains the canescence powder after hydrochloric acid cleaning; Use distilled water and dehydrated alcohol to clean 3 times ~ 5 times to the canescence powder after hydrochloric acid cleaning respectively successively, then at temperature is 60 DEG C ~ 90 DEG C dry 3h ~ 5h, obtain α-AlH
3powder;
The massfraction of the hydrochloric acid soln described in step 4 is 1% ~ 10%;
The quality of canescence powder described in step 4 and the volume ratio 5g:50mL of hydrochloric acid soln;
α-AlH described in step 4
3the particle diameter of powder is 20 μm ~ 30 μm.
2. one according to claim 1 is from nanometer AlH
3α-AlH is extracted in/metal chloride
3the method of powder, is characterized in that the AlH described in step one
3/ MgCl
2nano-complex powder is prepared according to the following steps:
The magnesium alloy powder of 1., to be the magnesium dust of 0.1mm ~ 2mm or granularity by granularity be 0.1mm ~ 2mm is placed in ball grinder, be (30 ~ 120) in ball material mass ratio: the ratio of 1 puts into abrading-ball, in a hydrogen atmosphere with the speed ball milling 15h ~ 20h of 250r/min ~ 400r/min, obtain the nanocrystalline M gH that grain-size is 9nm ~ 11nm, powder size is 1 μm ~ 10 μm
2powder;
Step 1. described in magnesium alloy be ZK60; In described ZK60, Mg content is 93.5%, Zn content be 6%, Zr content is 0.5%;
2., ball milling, reaction: be first 9nm ~ 11nm by grain-size, powder size is the nanocrystalline M gH of 1 μm ~ 10 μm
2powder and AlCl
3powder mixes, and is then placed in ball grinder, is (30 ~ 120): the ratio of 1 puts into abrading-ball in ball material mass ratio; Again under hydrogen atmosphere and pressure are the condition of 0.2MPa ~ 1.0MPa, carry out ball milling with the speed of 250r/min ~ 400r/min, Ball-milling Time 15 ~ 30h, obtains AlH
3/ MgCl
2nano-complex powder;
Step 2. described in grain-size be 9nm ~ 11nm, powder size is the nanocrystalline M gH of 1 μm ~ 10 μm
2the amount of substance of powder and AlCl
3the amount of substance of powder is than being (2.7 ~ 3.2): 2.
3. one according to claim 1 is from nanometer AlH
3α-AlH is extracted in/metal chloride
3the method of powder, is characterized in that the AlH described in step one
3/ LiCl nano-complex powder is prepared according to the following steps:
1., LiAlH is taken
4, AlCl
3and LiBH
4;
Step 1. described in LiAlH
4with AlCl
3mol ratio be (2.8 ~ 3.2): 1;
Step 1. described in LiBH
4with AlCl
3mol ratio be (2 ~ 10): 1;
2., by step 1. in the LiAlH that takes
4, AlCl
3and LiBH
4be dissolved into respectively in three parts of ether, obtain LiAlH
4diethyl ether solution, AlCl
3diethyl ether solution and LiBH
4diethyl ether solution;
Step 2. described in LiAlH
4liAlH in diethyl ether solution
4be 1:(20 ~ 50 with the mol ratio of ether);
Step 2. described in AlCl
3alCl in diethyl ether solution
3be 1:(20 ~ 50 with the mol ratio of ether);
Step 2. described in LiBH
4liBH in diethyl ether solution
4be 1:(20 ~ 50 with the mol ratio of ether);
3. the LiAlH, 2. step obtained
4diethyl ether solution, AlCl
3diethyl ether solution and LiBH
4diethyl ether solution mixes, then low whipping speed is stir 10min ~ 20min under 250r/min ~ 400r/min, obtains mixing solutions; Mixing solutions is heated to 35 DEG C ~ 45 DEG C, then reacts 20min ~ 60min at temperature is 35 DEG C ~ 45 DEG C, then carry out underpressure distillation, remove ether, obtain AlH
3/ LiCl nano-complex powder;
Step 3. described in LiAlH
4diethyl ether solution, AlCl
3diethyl ether solution and LiBH
4the volume ratio of diethyl ether solution is 1:1:1.
4. one according to claim 1 is from nanometer AlH
3α-AlH is extracted in/metal chloride
3the method of powder, is characterized in that the solvent described in step one is ether or ether/toluene mixture liquid; Described ether/toluene mixture liquid is mixed by ether and toluene, and the volume ratio of ether and toluene is (1 ~ 5): 1.
5. one according to claim 1 is from nanometer AlH
3α-AlH is extracted in/metal chloride
3the method of powder, is characterized in that nanometer AlH in step one
3/ metal chloride joins in solvent, then low whipping speed is stir 10min ~ 30min under 60r/min ~ 80r/min, obtains the metal-salt of solid phase and the AlH of liquid phase
3the diethyl ether solution of etherate.
6. one according to claim 1 is from nanometer AlH
3α-AlH is extracted in/metal chloride
3the method of powder, is characterized in that nanometer AlH in step one
3/ metal chloride joins in solvent, then low whipping speed is stir 30min ~ 90min under 80r/min ~ 100r/min, obtains the metal-salt of solid phase and the AlH of liquid phase
3the diethyl ether solution of etherate.
7. one according to claim 1 is from nanometer AlH
3α-AlH is extracted in/metal chloride
3the method of powder, is characterized in that in step 3 under anhydrous and oxygen-free condition, uses the AlH of liquid phase that cold-trap will obtain in step 2
3ether in the diethyl ether solution of etherate is drained, and obtains AlH
3etherate; By AlH
3etherate vacuum tightness be 40Pa ~ 50Pa, turn a brilliant temperature be 50 DEG C ~ 90 DEG C at turn brilliant 2h ~ 8h, obtain canescence powder.
8. one according to claim 1 is from nanometer AlH
3α-AlH is extracted in/metal chloride
3the method of powder, is characterized in that in step 3 under anhydrous and oxygen-free condition, uses the AlH of liquid phase that cold-trap will obtain in step 2
3ether in the diethyl ether solution of etherate is drained, and obtains AlH
3etherate; By AlH
3etherate vacuum tightness be 40Pa ~ 50Pa, turn a brilliant temperature be 90 DEG C ~ 120 DEG C at turn brilliant 8h ~ 12h, obtain canescence powder.
9. one according to claim 1 is from nanometer AlH
3α-AlH is extracted in/metal chloride
3the method of powder, is characterized in that the massfraction of the hydrochloric acid soln described in step 4 is 1% ~ 5%.
10. one according to claim 1 is from nanometer AlH
3α-AlH is extracted in/metal chloride
3the method of powder, is characterized in that the massfraction of the hydrochloric acid soln described in step 4 is 5% ~ 10%.
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| 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 |
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| KR20090044883A (en) * | 2007-11-01 | 2009-05-07 | 한국에너지기술연구원 | Production of aluminum hydride type hydrogen storage material by mechnochemical method |
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