CN109052440B - A method of four ammonium aluminum fluorides of production and side product sodium chloride - Google Patents
A method of four ammonium aluminum fluorides of production and side product sodium chloride Download PDFInfo
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- CN109052440B CN109052440B CN201810897570.3A CN201810897570A CN109052440B CN 109052440 B CN109052440 B CN 109052440B CN 201810897570 A CN201810897570 A CN 201810897570A CN 109052440 B CN109052440 B CN 109052440B
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- aluminum fluorides
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- -1 ammonium aluminum fluorides Chemical class 0.000 title claims abstract description 58
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 239000006227 byproduct Substances 0.000 title claims abstract description 15
- 239000011780 sodium chloride Substances 0.000 title claims abstract description 14
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 52
- 238000000498 ball milling Methods 0.000 claims abstract description 47
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 43
- 238000010438 heat treatment Methods 0.000 claims description 24
- 235000019270 ammonium chloride Nutrition 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 230000008676 import Effects 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 32
- 238000002441 X-ray diffraction Methods 0.000 description 21
- 239000003570 air Substances 0.000 description 13
- 239000012467 final product Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 9
- 239000012300 argon atmosphere Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000012159 carrier gas Substances 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229910020027 (NH4)3AlF6 Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910017665 NH4HF2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- TWJVNKMWXNTSAP-UHFFFAOYSA-N azanium;hydroxide;hydrochloride Chemical compound [NH4+].O.[Cl-] TWJVNKMWXNTSAP-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000037 vitreous enamel Substances 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
- C01F7/788—Ammonium aluminium fluorides, e.g. ammonium hexafluoroaluminate
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a kind of four ammonium aluminum fluorides of production and the methods of side product sodium chloride, and using ammonium acid fluoride and aluminium chloride as raw material, four ammonium aluminum fluorides are prepared after mixing and ball milling is reacted and is heat-treated；The molar ratio of ammonium acid fluoride and aluminium chloride is 3:1.The invention discloses a kind of four ammonium aluminum fluorides of production and the method for side product sodium chloride, this method, which has, to be implemented simple, with short production cycle, and four ammonium aluminum fluorides of synthesis, and simultaneously can side product sodium chloride without miscellaneous phase.
Description
Technical field
The present invention relates to fluorination four ammonium aluminum fluoride fields of work product, and in particular to a kind of four ammonium aluminum fluorides of production and by-product chlorine
Change the method for ammonium.
Background technique
Four ammonium aluminum fluoride (NH4AlF4) it is to prepare aluminum trifluoride (AlF3) persursor material, be heated to 400 DEG C i.e.
Produce aluminum trifluoride [Xian-Wei HU etc., Transactions of Nonferrous Metals Society of
China, 2011,21 (9), 2087-2092], aluminum trifluoride in aluminium electrolytic industry to reduce electrolyte fusion temperature and
Improve conductivity, the flux as nonferrous metal, component and the essential oil production of the fluxing agent and glaze of ceramic glaze and vitreous enamel
The inhibitor [https: //baike.sogou.com/v68980755.htm of middle side fermentation? fromTitle=is borontrifluoride
Aluminium].
Separately it has been reported that following for electrode material can be improved after cobalt acid lithium anode material surface coats four ammonium aluminum fluorides
Ring performance and high rate performance [Amine R etc., Electrochemical and Solid-State Letters, 2010,13
(8), A101-A104.].
Currently, the method for four ammonium aluminum fluoride of preparation on the books in document is wet chemistry method.
Such as, by nine water aluminum nitrate (Al (NO of high concentration3)3·9H2O) solution is mixed with ammonium fluoride solution, is protected at 80 DEG C
Temperature stirs, and subsequent filtering is made for dry 24 hours, this method four ammonium aluminum fluoride production cycles of preparation length [C.Alonso etc.,
Chemistry of Materials, 2000,12 (4): 1148-1155].
For another example, the side of four ammonium aluminum fluorides is prepared using hexafluorophosphoric acid 1- ethyl-3-methylimidazole, aluminium isopropoxide and phosphoric acid
Method needs first to prepare presoma 1-ethyl-3-methyllimidazolium bromide, prepares hexafluorophosphoric acid 1- ethyl-3-methylimidazole with this, so
It mixes heat preservation with aluminium isopropoxide and phosphoric acid at 190 DEG C afterwards and obtains four ammonium aluminum fluorides in 96 hours, preparation process is cumbersome, preparation time
Long [E.R.Parnham etc., Journal of Solid State Chemistry, 180 (2007), 49-53].
And industrial aspect does not prepare the record and method of four ammonium aluminum fluorides directly so far.Therefore, it develops and to be simple and efficient
The method for preparing four ammonium aluminum fluorides is extremely necessary.
Summary of the invention
The invention discloses a kind of four ammonium aluminum fluorides of production and the method for side product sodium chloride, this method have implement it is simple,
It is with short production cycle, four ammonium aluminum fluorides of synthesis without miscellaneous phase, and can simultaneously side product sodium chloride.
Specific technical solution is as follows:
A method of four ammonium aluminum fluorides of production and side product sodium chloride, using ammonium acid fluoride and aluminium chloride as raw material, through mixing
Four ammonium aluminum fluorides are prepared after ball-milling reaction and heat treatment；
The molar ratio of the ammonium acid fluoride and aluminium chloride is 3:1.
The present invention by the way of physics ball milling, is prepared into using the ammonium acid fluoride of special molar ratio and aluminium chloride as raw material
To four ammonium aluminum fluorides.
It is found through experiment that will lead to impurity, such as hexafluoro aluminic acid when the molar ratio of ammonium acid fluoride and aluminium chloride is not 3:1
Ammonium ((NH4)3AlF6) generation, to reduce the purity of four ammonium aluminum fluoride of final product.
It is carried out under mixing and ball milling reaction, inert atmosphere at room temperature or vacuum environment.
Preferably, the mixing and ball milling reaction, ratio of grinding media to material are 60~120:1, and rotational speed of ball-mill is 400~500 revs/min,
Ball-milling Time is 1~2 hour.
Under the premise of guaranteeing the molar ratio of ammonium acid fluoride and aluminium chloride is 3:1, using above-mentioned preferred ball-milling reaction item
It is the mixture of four ammonium aluminum fluorides and ammonium chloride that part, which can guarantee that mixing and ball milling reaction is prepared,.
Preferably, the temperature of the heat treatment is 200~300 DEG C, and soaking time is 4~6 hours；Further preferably, institute
The heating rate for stating heat treatment is 5~20 DEG C/min.
NH in heat treatment process4The decomposition reaction that Cl occurs is shown below:
NH4Cl→NH3↑+HCl↑；
The gas generated after heat treatment is NH3With the gaseous mixture of HCl, by the gaseous mixture by carrier gas (air, nitrogen or
Argon gas) imported into deionized water after aqueous ammonium chloride solution can be obtained, recycled after recycling.
Remaining solid powder is cooled to room temperature to get four ammonium aluminum fluoride is arrived after heat treatment.
It is tested through X-ray diffraction, four ammonium aluminum fluorides of no miscellaneous phase, X-ray diffraction can be obtained in preparation method of the invention
Analysis only finds the diffraction maximum of four ammonium aluminum fluorides, does not find the diffraction maximum of other phases.
Compared with prior art, the present invention has the advantage that
The production method of four ammonium aluminum fluoride disclosed by the invention, easy to operate, with short production cycle, required raw material fluorinated hydrogen ammonium
Cheap and easy to get with aluminium chloride, four ammonium aluminum fluorides of preparation purity is high does not detect miscellaneous phase, at the same can side product sodium chloride be used for phase
Answer industrial circle.Therefore, the extremely suitable industrialized production of the production method.
Detailed description of the invention
Fig. 1 is the x-ray diffraction pattern of 1 ball milling product of embodiment, and the XRD spectrum for providing ammonium acid fluoride and aluminium chloride is made
For comparison；
Fig. 2 is the x-ray diffraction pattern of final product prepared by embodiment 1；
Fig. 3 is the stereoscan photograph of final product prepared by embodiment 1；
Fig. 4 is the x-ray diffraction pattern of ball milling product, final product in comparative example 1, and provides ammonium acid fluoride and aluminium chloride
XRD spectrum as a comparison；
Fig. 5 is the x-ray diffraction pattern of ball milling product, final product in comparative example 2；
Fig. 6 is the x-ray diffraction pattern of ball milling product, final product in comparative example 3；
Fig. 7 is the x-ray diffraction pattern of ball milling product, final product in embodiment 2；
Fig. 8 is the x-ray diffraction pattern of ball milling product, final product in comparative example 4.
Specific embodiment
Embodiment 1
(1) because facile hydrolysis is rotten in air for aluminium chloride, therefore in argon atmosphere glove box, by ammonium acid fluoride and aluminium chloride
It is placed in stainless steel jar mill and seals according to molar ratio 3:1 mixing, ratio of grinding media to material 120:1.
(2) ball grinder equipped with ammonium acid fluoride and aluminum chloride mixture was obtained with revolving speed ball milling 1 hour of 500 revs/min
To mixture.
Fig. 1 is X-ray diffraction (XRD) map of ball-milled mixtures, and analysis finds do not have initial reactant fluorine in mixture
Change the diffraction maximum of hydrogen ammonium and aluminium chloride, the only diffraction maximum of four ammonium aluminum fluorides and ammonium chloride.Initial reactant ammonium acid fluoride and chlorine
The XRD spectrum for changing aluminium is also found in Fig. 1.Illustrate initial reactant total overall reaction, the mixture of generation be four ammonium aluminum fluorides with
Ammonium chloride.
(3) product (mixtures of four ammonium aluminum fluorides and ammonium chloride) after ball milling is placed in the tube furnace for being connected with atmospheric carrier air
In, carrier gas is passed through in deionized water.Product is warming up to 250 DEG C with the heating rate of 10 DEG C/min after ball milling, keeps the temperature 4 hours, chlorine
Change ammonium and decompose volatilization, ammonium chloride water can be obtained after importing deionized water by atmospheric carrier air in the ammonia and hydrogen chloride gas of generation
Solution, it is stand-by after recycling.It is four ammonium aluminum fluorides after remaining solid product is cooling.
The XRD spectrum of product is listed in Fig. 2, the only diffraction maximum of four ammonium aluminum fluorides, and ammonium chloride all decomposes volatilization, generates
Four ammonium aluminum fluoride of high-purity without miscellaneous phase.
Fig. 3 is the scanning electron microscope pattern photo of four ammonium aluminum fluoride manufactured in the present embodiment, primary particle having a size of 50~
100nm, due to nano effect, there are a degree of reunions for product grain, and the particle size after reunion is micron and sub-micron
Grade.
Comparative example 1
(1) in argon atmosphere glove box, ammonium acid fluoride is mixed with aluminium chloride according to molar ratio 3:1 and is placed in stainless steel ball
It is sealed in grinding jar, ratio of grinding media to material 120:1.
(2) ball grinder equipped with ammonium acid fluoride and aluminum chloride mixture was obtained with revolving speed ball milling 1 hour of 500 revs/min
To the mixture of four ammonium aluminum fluorides and ammonium chloride.
(3) product (mixtures of four ammonium aluminum fluorides and ammonium chloride) after ball milling is placed in the batch-type furnace of ventilating air,
160 DEG C are warming up to the heating rate of 10 DEG C/min, keeps the temperature 4 hours, it is then cooling in air atmosphere.
Fig. 4 is the XRD spectrum of product and original ammonium acid fluoride and aluminium chloride after ball milling product and heat treatment.As it can be seen that
Have apparent four ammonium aluminum fluorides diffraction maximum in map, but with the diffraction maximum of ammonium chloride, show 160 DEG C at a temperature of keep the temperature 4
Hour, ammonium chloride can not be completely removed.
Comparative example 2
In argon atmosphere glove box, ammonium acid fluoride is mixed with aluminium chloride according to molar ratio 4:1 and is placed in stainless steel ball-milling
It is sealed in tank, ratio of grinding media to material 120:1, with revolving speed ball milling 2 hours of 500 revs/min, the product after ball milling is placed in ventilating air
Batch-type furnace in, be warming up to 250 DEG C with the heating rate of 5 DEG C/min, keep the temperature 6 hours, it is then cooling in air atmosphere, obtain
Final product.
Fig. 5 is the XRD spectrum of final product after this comparative example ball milling product and heat treatment.It can be seen that from analysis result
After ball-milling reaction, ammonium acid fluoride and aluminium reaction are in addition to generating four ammonium aluminum fluorides and ammonium chloride, and there are also unreacteds in product
NH4HF2And (the NH that reaction generates4)3AlF6, after heating at 250 DEG C, product NH4AlF4With NH4Cl、
NH4ClF4Mixture.
Comparative example 3
In argon atmosphere glove box, ammonium acid fluoride is mixed with aluminium chloride according to molar ratio 3:1 and is placed in stainless steel ball-milling
It is sealed in tank, ratio of grinding media to material 30:1, with revolving speed ball milling 3 hours of 350 revs/min, the product after ball milling is placed in ventilating air
Batch-type furnace in, be warming up to 250 DEG C with the heating rate of 5 DEG C/min, keep the temperature 4 hours, it is then cooling in air atmosphere, obtain
Final product.
Fig. 6 is the XRD spectrum of final product after ball milling product, heat treatment in this comparative example.It can from analysis result
Out after ball-milling reaction, ammonium acid fluoride and aluminium reaction also generate in product in addition to generating four ammonium aluminum fluorides and ammonium chloride
(NH4)3AlF6, after heating at 250 DEG C, product NH4AlF4With NH4The mixture of Cl.
Embodiment 2
In argon atmosphere glove box, ammonium acid fluoride is mixed with aluminium chloride according to molar ratio 3:1 and is placed in stainless steel ball-milling
It is sealed in tank, ratio of grinding media to material 60:1, with revolving speed ball milling 2 hours of 400 revs/min, the product after ball milling is placed in ventilating air
Batch-type furnace in, be warming up to 200 DEG C with the heating rate of 2 DEG C/min, keep the temperature 4 hours, it is then cooling in air atmosphere, obtain
Four ammonium aluminum fluoride products.
Fig. 7 is final product and original ammonium acid fluoride and aluminium chloride after ball milling product, heat treatment in the present embodiment
XRD spectrum.It can be seen that after ball-milling reaction from analysis result, ammonium acid fluoride reacts completely with aluminium chloride generates four ammonium aluminum fluorides
With ammonium chloride, through heating at 200 DEG C, the product that ammonium chloride obtains after decomposing is four ammonium aluminum fluorides, and XRD detection and analysis are not sent out
The diffraction maximum of existing other products.
Comparative example 4
In argon atmosphere glove box, ammonium acid fluoride is mixed with aluminium chloride according to molar ratio 3:1 and is placed in stainless steel ball-milling
It is sealed in tank, ratio of grinding media to material 60:1, with revolving speed ball milling 2 hours of 400 revs/min, obtained ball milling product was four ammonium aluminum fluorides
With ammonium chloride.Ball milling product is placed in the batch-type furnace of ventilating air again, 200 DEG C is warming up to the heating rate of 2 DEG C/min, protects
Temperature 3 hours, remaining solid
The XRD spectrum of product is listed in Fig. 8, it is seen then that in addition to obtaining four ammonium aluminum fluorides, there is also a small amount of impurity.Illustrate 200
3 hours are kept the temperature at DEG C, is not enough to completely remove ammonium chloride.
Embodiment 3
In argon atmosphere glove box, ammonium acid fluoride is mixed with aluminium chloride according to molar ratio 3:1 and is placed in stainless steel ball-milling
It is sealed in tank, ratio of grinding media to material 120:1, with revolving speed ball milling 1 hour of 500 revs/min, the product after ball milling is placed in and is connected with nitrogen
In the tube furnace of carrier gas, carrier gas is passed through in deionized water, and tube furnace is warming up to 300 DEG C with the heating rate of 20 DEG C/min, is protected
Temperature 6 hours.
Through X-ray diffraction analysis it is found that after ball milling, primary sample reacts completely generates four ammonium aluminum fluorides and ammonium chloride,
After only discovery has the diffraction maximum of four ammonium aluminum fluorides, ammonium chloride to decompose volatilization in the product obtained after being heat-treated at 300 DEG C, generation
The mixed gas of hydrogen chloride and ammonia is passed through in deionized water with carrier gas obtains aqueous ammonium chloride solution.
Claims (5)
1. the method for a kind of four ammonium aluminum fluorides of production and side product sodium chloride, which is characterized in that with ammonium acid fluoride and aluminium chloride be original
Four ammonium aluminum fluorides are prepared after mixing and ball milling is reacted and is heat-treated in material, and the tail gas generated after heat treatment imports deionized water
After obtain aqueous ammonium chloride solution, recycled after recycling；The molar ratio of the ammonium acid fluoride and aluminium chloride is 3:1；The mixing ball
Mill reaction, ratio of grinding media to material are 60~120:1, and rotational speed of ball-mill is 400~500 revs/min；The temperature of the heat treatment is 200~300
DEG C, soaking time is 4~6 hours.
2. the method for four ammonium aluminum fluorides of production according to claim 1 and side product sodium chloride, which is characterized in that the mixing
It is carried out under ball-milling reaction, inert atmosphere at room temperature or vacuum environment.
3. the method for four ammonium aluminum fluorides of production according to claim 1 and side product sodium chloride, which is characterized in that the mixing
Ball-milling reaction, Ball-milling Time are 1~2 hour.
4. the method for four ammonium aluminum fluorides of production according to claim 1 and side product sodium chloride, which is characterized in that at the heat
The heating rate of reason is 5~20 DEG C/min.
5. the method for four ammonium aluminum fluorides of production according to claim 1 and side product sodium chloride, which is characterized in that will be heat-treated
Remaining solid powder is cooled to room temperature to get four ammonium aluminum fluoride is arrived afterwards.
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| CN201810897570.3A CN109052440B (en) | 2018-08-08 | 2018-08-08 | A method of four ammonium aluminum fluorides of production and side product sodium chloride |
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| CN109052440B true CN109052440B (en) | 2019-08-27 |
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