CN105417562B - A kind of preparation method of hydro-thermal method synthesis alpha-aluminium oxide - Google Patents
A kind of preparation method of hydro-thermal method synthesis alpha-aluminium oxide Download PDFInfo
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- CN105417562B CN105417562B CN201510998671.6A CN201510998671A CN105417562B CN 105417562 B CN105417562 B CN 105417562B CN 201510998671 A CN201510998671 A CN 201510998671A CN 105417562 B CN105417562 B CN 105417562B
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- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 title claims description 20
- 239000002245 particle Substances 0.000 claims abstract description 65
- 239000004411 aluminium Substances 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 28
- 239000013078 crystal Substances 0.000 claims abstract description 27
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 229910052594 sapphire Inorganic materials 0.000 claims description 52
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 28
- 229910052782 aluminium Inorganic materials 0.000 claims description 27
- 229910006636 γ-AlOOH Inorganic materials 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 15
- 238000009938 salting Methods 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 230000007062 hydrolysis Effects 0.000 claims description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- 239000011812 mixed powder Substances 0.000 claims description 10
- 239000011268 mixed slurry Substances 0.000 claims description 10
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910003145 α-Fe2O3 Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 13
- 229910052593 corundum Inorganic materials 0.000 abstract description 11
- 238000009826 distribution Methods 0.000 abstract description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052744 lithium Inorganic materials 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 3
- 230000007704 transition Effects 0.000 abstract description 3
- 230000007812 deficiency Effects 0.000 abstract description 2
- 229910002706 AlOOH Inorganic materials 0.000 abstract 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 239000000047 product Substances 0.000 description 10
- 238000012545 processing Methods 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 238000009413 insulation Methods 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000012808 vapor phase Substances 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
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
- C01F7/447—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by wet processes
- C01F7/448—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by wet processes using superatmospheric pressure, e.g. hydrothermal conversion of gibbsite into boehmite
-
- 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
- C01P2004/51—Particles with a specific particle size distribution
-
- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention use hydro-thermal method, and toward addition crystal seed α Al in the hydroxide sol of product aluminium2O3, mainly obtain under reactor high temperature and high pressure environment that particle diameter is small, and particle diameter distribution is narrow first with hydro-thermal reaction, the high γ AlOOH powders of sintering activity.Again by less than α Al2O3The calcining heat (800~1150 DEG C) that 1200 DEG C of phase transition temperature finally synthesizes α Al2O3.The α Al of synthesis2O3Particle dispersion is high, and particle diameter distribution is narrow, is 1~20m than surface2/ g, average grain diameter high purity 99.99%, can apply to lithium battery diaphragm coated ceramic material, laser host material, semiconducting matrix material, high pressure component, optics and various Precision Machinery Elements etc. in 350~500nm.Be uniformly dispersed it is an object of the invention to provide a kind of particle, particle diameter it is small, the α Al of high-purity2O3Preparation method, this method can solve the problem that the deficiency on existing industrial manufacture process, reduce energy consumption, simplify technique, improving production efficiency, prepared α Al2O3Purity is high, and particle diameter is small, dispersed height, and particle diameter distribution is narrow.
Description
Technical field
The present invention relates to technical field of inorganic nonmetallic materials, more particularly to a kind of preparation of hydro-thermal method synthesis Alpha-alumina
Method.
Background technology
α-Al2O3It is corundum (Corundum) structure, belongs to trigonal system.α-Al2O3A kind of important inorganic non-gold of material
Belong to material, chemical property is stable, and corrosion-resistant and electrical insulating property is excellent.With molten point high (2050 DEG C), (Mohs is hard for hardness height
The features such as degree is 9), compact structure, intensity are high, wearability is good, thus it is widely used in lithium battery diaphragm coated ceramic material, ceramic material
Material, semi-conducting material, surface preventing material, biomaterial, optical material, refractory material, the field such as substrate of surface-mounted integrated circuit.
As in recent years, the fast development of the industry such as electronic communication, electronic material is also increasingly paid attention to by everybody.By
In α-Al2O3Excellent physical, chemical property, it is also widely used in the field of some new developments.Such as material is coated in battery diaphragm
Expect this respect, α-Al2O3It is widely used, in the market even there are the α-Al being exclusively used in terms of battery diaphragm coating material2O3Production
Product.Last layer α-Al are applied on barrier film2O3After coating, short circuit between electrode can be effectively avoided, improves the safety that lithium battery uses
Property.
In recent years, α-Al2O3Product technology of preparing has obtained faster development, many new synthetic methods occurs, such as solid
Xiang Fa, vapor phase method, chemical precipitation method, sol-gel process, hydro-thermal method etc..Chemical precipitation method prepare aluminum oxide such as Chinese patent
The A of publication number CN 104229846 are used as raw material by activating fly ash, obtain aluminum oxide by precipitation, advantage is from activation powder
Al elements are extracted in coal ash and aluminum oxide is prepared, but prepared aluminum oxide purity is not high-purity, and calcine
Temperature is up to 1200 degree, and power consumption is more serious, and the aluminum oxide of gained is reunited seriously.The A of China Patent Publication No. CN 102826579
Ultra-pure, superfine alumina powder is prepared as raw material using aluminium flake and isopropanol, but reparation technology complexity is cumbersome, cost
It is high.Aluminium salt is calcined and obtained by using two steps annealing method by the A of China Patent Publication No. CN 101200300 in reducing atmosphere
α-Al2O3.Due to taking multiple calcining, and calcination atmosphere is different, it will increase energy consumption, and complex steps；And add when calcining
Enter carbon black, it will make obtained α-Al2O3Product purity declines, and impurity increases.
And the present invention uses hydro-thermal method, increased using presoma in the rise of the solubility with temperature of the reactor of sealing
Add, because the solubility of predecessor or intermediate product solvable in high-temperature high pressure water is more than corresponding steady oxide in water
Solubility, ultimately result in solution supersaturation and form more stable γ-AlOOH and α-Al2O3Deng mix products, so as to main
High γ-AlOOH the products of sintering activity are obtained, then by less than α-Al2O3The calcining heat of phase transition temperature (800~1150 DEG C)
Final synthesis α-Al2O3Product.α-the Al of synthesis2O3Powder granule dispersiveness is high, and particle diameter distribution is narrow, is 1~20m than surface2/ g,
Average grain diameter high purity 99.99%, can apply to lithium battery diaphragm coated ceramic material, laser-based in 350~500nm
Material, semiconducting matrix material, high pressure component, optics and various Precision Machinery Elements etc..
The content of the invention
Be uniformly dispersed it is an object of the invention to provide a kind of particle, particle diameter it is small, the α-Al of high-purity2O3Preparation method, the party
Method can solve the problem that the deficiency on existing industrial manufacture process, reduces energy consumption, simplifies technique, improving production efficiency, prepared α-
Al2O3Purity is high, and particle diameter is small, dispersed height, and particle diameter distribution is narrow.
The present invention provides a kind of preparation method of hydro-thermal method synthesis Alpha-alumina, comprises the following steps：
(a) Al salt is dissolved in pure water, and salting liquid is made after quick stirring；
(b) by Al3+Salting liquid be added dropwise in the ammonia spirit quickly stirred and be hydrolyzed；
(c) most of moisture that aluminum hydroxide sol is removed after reacting obtains aluminium presoma, and toward adding in aluminium presoma
Crystal seed；
(d) aluminium presoma and seed particles reslurry are disperseed using high speed beater；
(e) aluminium presoma is put into reactor, added between the 60~80% of compactedness；
(f) reactor is heated up under fast stirring and is heated to 100~220 DEG C, after being incubated 1~10 hour, Temperature fall；
(g) γ-AlOOH, the α-Al obtained (f) step2O3It is spray-dried after being washed Deng mixed slurry；
(h) by γ-AlOOH, α-Al2O3It being put into kiln Deng mixed powder and calcined, calcining heat is 800~1150 DEG C,
1~10h is calcined, α-Al are obtained after Temperature fall2O3Powder；
(i) by the α-Al of reunion2O3Powder carries out air-flow smashing, is uniformly dispersed, high-purity α-Al2O3Powder.
Preferably, preparation method of the invention：
Above-mentioned steps (a) Al salt is Al (NO3)3·9H2O、AlCl3·6H2O、Al2(SO4)3·18H2O etc., preferably Al
(NO3)3·9H2O。
Above-mentioned steps (b) hydrolyze when water cooling and control solution temperature be less than 50 DEG C；Ammoniacal liquor molar concentration be 2.0~
8.0mol·L-1Between；Ammoniacal liquor and Al3+Mol ratio be 2:1~12:1；Solution ph control is 8.0~11.0 after hydrolysis
Between；Al is added dropwise3+The salting liquid time be added dropwise in 3~15min, preferably 5~8min.
The mode that the moisture of aluminum hydroxide sol is removed in above-mentioned steps (c) is dehydrated for filtering, press filtration or dewaterer.
It is α-Al that crystal seed is added in above-mentioned steps (c)2O3、TiO2、α-Fe2O3、SiO2、α-Cr2O3, MgO etc. it is a kind of or several
Kind particle, preferably α-Al2O3。
The particle size range of seed particles is added in above-mentioned steps (c) between 20~600nm, preferably 30~150nm.
It is 99.99% that crystal seed purity is added in above-mentioned steps (c), and the particle of crystal seed must be monodispersed particle；Add
The mass range of crystal seed is theoretical synthesis α-Al2O3The 0.1~10% of quality.
It can choose whether to divide seed particles in advance according to being actually needed before adding seed particles in above-mentioned steps (c)
Dissipate processing, to ensure that the seed particles added are monodisperse particles, pre-dispersed processing can select ultrasonic disperse, ball milling it is scattered,
It is sanded scattered etc..
In above-mentioned steps (e) can according to be actually needed choose whether add mineralizer, mineralizer can select KOH,
NH4The materials such as OH, NaOH, KBr, preferably NH4OH is as mineralizer；The addition molal quantity of mineralizer for theoretical synthesis α-
Al2O3The 0.05%~0.8% of molal quantity.
The concentration of aluminium presoma is 0.1~2.0molL in mixed liquor in reactor in above-mentioned steps (e)-1, it is preferably
0.3~1.0molL-1。
Above-mentioned steps (f) heating rate control between 0.5~5.0 DEG C/min, preferably heating rate 1.0~3.0 DEG C/
min；Reactor mixing speed is preferably 500~1200rpm.
Furnace heating-up speed control is in 2~10 DEG C/min, preferably 3~6 DEG C/min in above-mentioned steps (h).
According to the present invention, it can synthesize and obtain the α-Al of high-purity2O3, it is characterised in that the α-Al2O3Powder surface area per unit volume
For 1~20m2/ g, average grain diameter is in 350~500nm, α-Al2O3Purity is more than 99.99%, and particle is uniformly dispersed, particle diameter divides
Cloth is narrow.
Unique distinction of the present invention is to use hydrothermal synthesis method, using presoma the reactor of sealing solubility with temperature
Rise and increase, because the solubility of predecessor or intermediate product solvable in high-temperature high pressure water is more than corresponding Stable Oxygen
Solubility of the compound in water, ultimately result in solution supersaturation and form more stable γ-AlOOH and α-Al2O3Produced Deng mixing
Thing, so as to mainly obtain the high γ-AlOOH products of sintering activity.Again by less than α-Al2O3Phase transition temperature (800~1150 DEG C)
Calcining heat finally synthesize α-Al2O3Product.α-the Al of synthesis2O3Powder granule dispersiveness is high, and particle diameter distribution is narrow, compares surface
For 1~20m2/ g, average grain diameter high purity 99.99%, can apply to lithium battery diaphragm coated ceramic in 350~500nm
Material, laser host material, semiconducting matrix material, high pressure component, optics and various Precision Machinery Elements etc..
Brief description of the drawings
Fig. 1 present invention process flow charts；
α-the Al of Fig. 2 step (i) synthesis of the present invention2O3The scanning electron microscopic picture of product；
α-the Al of Fig. 3 step (i) synthesis of the present invention2O3Product is coated in the scanning electron microscopic picture on lithium battery diaphragm surface.
Embodiment
To further illustrate present disclosure below in conjunction with specific embodiment and accompanying drawing, but the protection of the present invention
Scope is not limited only to the content described by embodiment.
Embodiment 1
(1) according to stoichiometric proportion precise Al (NO3)3·9H2O, put it into the quick stirring appearance for having filled pure water
In device, and make Al (NO3)3·9H2O is dissolved in pure water.
(2) by Al3+Salting liquid be added dropwise in the ammonia spirit of the high-purity quickly stirred and be hydrolyzed, ammoniacal liquor mole is dense
Spend for 4.8molL-1, ammoniacal liquor and Al3+Mol ratio be about 3.8:1；Simultaneously solution temperature is less than water cooling in control container during hydrolysis
50℃；The control of solution pH value is 9.2 or so after hydrolysis；Al is added dropwise3+The salting liquid time be added dropwise in 5min.
(3) most of moisture of aluminum hydroxide sol is removed after reacting using press filtration by the way of, and toward adding in aluminium presoma
Enter α-Al2O3Crystal seed, crystal seed carried out ultrasonic disperse processing before adding, to ensure that seed particles are monodisperse particles；Particle
For average particle size range between 40nm~60nm, crystal seed purity is 99.99%, add the mass range of crystal seed for theoretical synthesis α-
Al2O3The 4.8% of quality.
(4) aluminium presoma and seed particles reslurry are disperseed using high speed beater.
(5) aluminium presoma is put into reactor, the concentration of aluminium presoma is 0.55molL in mixed liquor in reactor-1；And add NH4For OH as mineralizer, the addition molal quantity of mineralizer is theoretical synthesis α-Al2O3The 0.1% of molal quantity.
(6) reactor is heated up under fast stirring and is heated to 190 DEG C, heating rate is controlled in 1.8 DEG C/min；Reactor
Mixing speed is preferably 1100rpm；After insulation 4 hours, Temperature fall, γ-AlOOH, α-Al are obtained2O3Deng mixed slurry.
(7) by obtained γ-AlOOH, α-Al2O3Deng mixed slurry wash after be spray-dried, obtain γ-AlOOH,
α-Al2O3Deng mixed powder；
(8) by γ-AlOOH, α-Al2O3It is put into kiln Deng mixed powder and is calcined, calcining heat is 1080 DEG C, heating
Speed control calcines 5h, α-Al is obtained after Temperature fall in 3.5 DEG C/min2O3Powder；
(9) by the α-Al of reunion2O3Powder carries out air-flow smashing, obtains α-Al2O3Powder surface area per unit volume is 6.1m2/ g, it is average
Particle diameter is about 320nm, and purity is more than 99.99%, particle is uniformly dispersed, particle diameter distribution is narrow α-Al2O3Powder.
Embodiment 2
(1) according to stoichiometric proportion precise Al (NO3)3·9H2O, put it into the quick stirring appearance for having filled pure water
In device, and make Al (NO3)3·9H2O is dissolved in pure water.
(2) by Al3+Salting liquid be added dropwise in the ammonia spirit of the high-purity quickly stirred and be hydrolyzed, ammoniacal liquor mole is dense
Spend for 4.0molL-1, ammoniacal liquor and Al3+Mol ratio be about 4.5:1；Simultaneously solution temperature is less than water cooling in control container during hydrolysis
50℃；The control of solution pH value is 9.5 or so after hydrolysis；Al is added dropwise3+The salting liquid time be added dropwise in 6min.
(3) most of moisture of aluminum hydroxide sol is removed after reacting using press filtration by the way of, and toward adding in aluminium presoma
Enter α-Al2O3Crystal seed, crystal seed carried out ball milling decentralized processing before adding, to ensure that seed particles are monodisperse particles；Particle
For average particle size range between 30nm~55nm, crystal seed purity is 99.99%, add the mass range of crystal seed for theoretical synthesis α-
Al2O3The 4.2% of quality.
(4) aluminium presoma and seed particles reslurry are disperseed using high speed beater.
(5) aluminium presoma is put into reactor, the concentration of aluminium presoma is 0.61molL in mixed liquor in reactor-1；And add NH4For OH as mineralizer, the addition molal quantity of mineralizer is theoretical synthesis α-Al2O3The 0.16% of molal quantity.
(6) reactor is heated up under fast stirring and is heated to 200 DEG C, heating rate is controlled in 2.0 DEG C/min；Reactor
Mixing speed is preferably 1000rpm；After insulation 4 hours, Temperature fall, γ-AlOOH, α-Al are obtained2O3Deng mixed slurry.
(7) by obtained γ-AlOOH, α-Al2O3Deng mixed slurry wash after be spray-dried, obtain γ-AlOOH,
α-Al2O3Deng mixed powder；
(8) by γ-AlOOH, α-Al2O3It is put into kiln Deng mixed powder and is calcined, calcining heat is 1100 DEG C, heating
Speed control calcines 5h, α-Al is obtained after Temperature fall in 3.8 DEG C/min2O3Powder；
(9) by the α-Al of reunion2O3Powder carries out air-flow smashing, obtains α-Al2O3Powder surface area per unit volume is 5.6m2/ g, it is average
Particle diameter is about 360nm, and purity is more than 99.99%, particle is uniformly dispersed, particle diameter distribution is narrow α-Al2O3Powder.
Embodiment 3
(1) according to stoichiometric proportion precise Al (NO3)3·9H2O, put it into the quick stirring appearance for having filled pure water
In device, and make Al (NO3)3·9H2O is dissolved in pure water.
(2) by Al3+Salting liquid be added dropwise in the ammonia spirit of the high-purity quickly stirred and be hydrolyzed, ammoniacal liquor mole is dense
Spend for 5.3molL-1, ammoniacal liquor and Al3+Mol ratio be about 3.8:1；Simultaneously solution temperature is less than water cooling in control container during hydrolysis
50℃；The control of solution pH value is 9.7 or so after hydrolysis；Al is added dropwise3+The salting liquid time be added dropwise in 5.5min.
(3) most of moisture of aluminum hydroxide sol is removed after reacting using press filtration by the way of, and toward adding in aluminium presoma
Enter α-Al2O3Crystal seed, crystal seed carried out ball milling decentralized processing before adding, to ensure that seed particles are monodisperse particles；Particle
For average particle size range between 20nm~50nm, crystal seed purity is 99.99%, add the mass range of crystal seed for theoretical synthesis α-
Al2O3The 5.1% of quality.
(4) aluminium presoma and seed particles reslurry are disperseed using high speed beater.
(5) aluminium presoma is put into reactor, the concentration of aluminium presoma is 0.63molL in mixed liquor in reactor-1；And add NH4For OH as mineralizer, the addition molal quantity of mineralizer is theoretical synthesis α-Al2O3The 0.2% of molal quantity.
(6) reactor is heated up under fast stirring and is heated to 200 DEG C, heating rate is controlled in 1.6 DEG C/min；Reactor
Mixing speed is preferably 980rpm；After insulation 5 hours, Temperature fall, γ-AlOOH, α-Al are obtained2O3Deng mixed slurry.
(7) by obtained γ-AlOOH, α-Al2O3Deng mixed slurry wash after be spray-dried, obtain γ-AlOOH,
α-Al2O3Deng mixed powder；
(8) by γ-AlOOH, α-Al2O3It is put into kiln Deng mixed powder and is calcined, calcining heat is 1065 DEG C, heating
Speed control calcines 6h, α-Al is obtained after Temperature fall in 3.8 DEG C/min2O3Powder；
(9) by the α-Al of reunion2O3Powder carries out air-flow smashing, obtains α-Al2O3Powder surface area per unit volume is 5.8m2/ g, it is average
Particle diameter is about 345nm, and purity is more than 99.99%, particle is uniformly dispersed, particle diameter distribution is narrow α-Al2O3Powder.
Embodiment 4
(1) according to stoichiometric proportion precise Al (NO3)3·9H2O, put it into the quick stirring appearance for having filled pure water
In device, and make Al (NO3)3·9H2O is dissolved in pure water.
(2) by Al3+Salting liquid be added dropwise in the ammonia spirit of the high-purity quickly stirred and be hydrolyzed, ammoniacal liquor mole is dense
Spend for 4.5molL-1, ammoniacal liquor and Al3+Mol ratio be about 4.1:1；Simultaneously solution temperature is less than water cooling in control container during hydrolysis
50℃；The control of solution pH value is 9.3 or so after hydrolysis；Al is added dropwise3+The salting liquid time be added dropwise in 7min.
(3) most of moisture of aluminum hydroxide sol is removed after reacting using press filtration by the way of, and toward adding in aluminium presoma
Enter α-Al2O3Crystal seed, crystal seed carried out ultrasonic disperse processing before adding, to ensure that seed particles are monodisperse particles；Particle
For average particle size range between 30nm~50nm, crystal seed purity is 99.99%, add the mass range of crystal seed for theoretical synthesis α-
Al2O3The 5.0% of quality.
(4) aluminium presoma and seed particles reslurry are disperseed using high speed beater.
(5) aluminium presoma is put into reactor, the concentration of aluminium presoma is 0.68molL in mixed liquor in reactor-1；And add NH4For OH as mineralizer, the addition molal quantity of mineralizer is theoretical synthesis α-Al2O3The 0.18% of molal quantity.
(6) reactor is heated up under fast stirring and is heated to 220 DEG C, heating rate is controlled in 2.2 DEG C/min；Reactor
Mixing speed is preferably 1100rpm；After insulation 4 hours, Temperature fall, γ-AlOOH, α-Al are obtained2O3Deng mixed slurry.
(7) by obtained γ-AlOOH, α-Al2O3Deng mixed slurry wash after be spray-dried, obtain γ-AlOOH,
α-Al2O3Deng mixed powder；
(8) by γ-AlOOH, α-Al2O3It is put into kiln Deng mixed powder and is calcined, calcining heat is 1125 DEG C, heating
Speed control calcines 5h, α-Al is obtained after Temperature fall in 4.0 DEG C/min2O3Powder；
(9) by the α-Al of reunion2O3Powder carries out air-flow smashing, obtains α-Al2O3Powder surface area per unit volume is 4.9m2/ g, it is average
Particle diameter is about 410nm, and purity is more than 99.99%, particle is uniformly dispersed, particle diameter distribution is narrow α-Al2O3Powder.
Above is having carried out specific elaboration to the present invention, it is used to help understand the present invention, but embodiments of the present invention
And be not restricted to the described embodiments, it is any without departing from the change made under the principle of the invention, modification, replacement, combination, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (9)
1. a kind of preparation method of hydro-thermal method synthesis Alpha-alumina, it is characterised in that comprise the following steps：
(a) Al salt is dissolved in pure water, and salting liquid is made after quick stirring；
(b) by Al3+Salting liquid be added dropwise in the ammonia spirit quickly stirred and be hydrolyzed；
(c) most of moisture that aluminum hydroxide sol is removed after reacting obtains aluminium presoma, and toward adding crystal seed in aluminium presoma；
(d) aluminium presoma and seed particles reslurry are disperseed using high speed beater；
(e) aluminium presoma is put into reactor, added between the 60~80% of compactedness；
(f) reactor is heated up under fast stirring and is heated to 100~220 DEG C, after being incubated 1~10 hour, Temperature fall；
(g) γ-AlOOH, the α-Al obtained (f) step2O3It is spray-dried after mixed slurry washing；
(h) by γ-AlOOH, α-Al2O3Mixed powder is put into kiln and calcined, and calcining heat is 800~1150 DEG C, calcining 1
~10h, α-Al are obtained after Temperature fall2O3Powder；
(i) by the α-Al of reunion2O3Powder carries out air-flow smashing, is uniformly dispersed, high-purity α-Al2O3Powder,
Water cooling and solution temperature is controlled to be less than 50 DEG C during the step (b) hydrolysis；Ammoniacal liquor molar concentration is 2.0~8.0molL-1
Between；Ammoniacal liquor and Al3+Mol ratio be 2:1~12:1；Solution ph control is between 8.0~11.0 after hydrolysis；Al is added dropwise3 +The salting liquid time be added dropwise in 3~15min,
The mode that the moisture of aluminum hydroxide sol is removed in the step (c) is dehydrated for filtering, press filtration or dewaterer,
The particle size range of seed particles is added in the step (c) between 20~600nm,
The step (e) can also further add mineralizer, and the mineralizer is selected from KOH, NH4OH, NaOH or KBr；Mineralising
The addition molal quantity of agent is theoretical synthesis α-Al2O3The 0.05%~0.8% of molal quantity,
The concentration of aluminium presoma is 0.1~2.0molL in mixed liquor in reactor in the step (e)-1,
Step (f) the heating rate control is between 0.5~5.0 DEG C/min；Reactor mixing speed is 500~1200rpm,
Furnace heating-up speed control is in 3~6 DEG C/min in the step (h).
2. preparation method according to claim 1, it is characterised in that step (a) the Al salt is selected from Al (NO3)3·
9H2O、AlCl3·6H2O or Al2(SO4)3·18H2O。
3. preparation method according to claim 1, it is characterised in that Al is added dropwise3+The salting liquid time dripped in 5~8min
Add complete.
4. preparation method according to claim 1, it is characterised in that crystal seed is added in the step (c) and is selected from α-Al2O3、
TiO2、α-Fe2O3、SiO2、α-Cr2O3, MgO it is one or two kinds of more than.
5. preparation method according to claim 1, it is characterised in that the particle diameter of seed particles is added in the step (c)
Scope is between 30~150nm.
6. preparation method according to claim 1, it is characterised in that crystal seed purity is added in the step (c) is
99.99%, the particle of crystal seed is monodispersed particle；The mass range for adding crystal seed is theoretical synthesis α-Al2O3The 0.1 of quality
~10%.
7. preparation method according to claim 1, it is characterised in that aluminium in mixed liquor in reactor in the step (e)
The concentration of presoma is 0.3~1.0molL-1。
8. preparation method according to claim 1, it is characterised in that step (f) heating rate control 1.0~
Between 3.0 DEG C/min.
9. preparation method according to claim 1, it is characterised in that furnace heating-up speed control is 3 in the step (h)
~6 DEG C/min.
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Denomination of invention: A hydrothermal synthesis method a- Preparation method of alumina Effective date of registration: 20231123 Granted publication date: 20180130 Pledgee: Bank of China Limited Shenzhen Luohu Branch Pledgor: Shenzhen Senior Technology Material Co.,Ltd. Registration number: Y2023980067292 |