CN117797754A - Device and method for preparing high-purity alumina micropowder by direct oxidation of liquid aluminum - Google Patents
Device and method for preparing high-purity alumina micropowder by direct oxidation of liquid aluminum Download PDFInfo
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- CN117797754A CN117797754A CN202311808132.2A CN202311808132A CN117797754A CN 117797754 A CN117797754 A CN 117797754A CN 202311808132 A CN202311808132 A CN 202311808132A CN 117797754 A CN117797754 A CN 117797754A
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- aluminum
- alumina
- liquid aluminum
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 160
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 158
- 239000007788 liquid Substances 0.000 title claims abstract description 113
- 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 89
- 238000000034 method Methods 0.000 title claims abstract description 79
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 55
- 230000003647 oxidation Effects 0.000 title claims abstract description 54
- 239000000843 powder Substances 0.000 claims abstract description 70
- 239000007789 gas Substances 0.000 claims abstract description 63
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000002844 melting Methods 0.000 claims abstract description 29
- 230000008018 melting Effects 0.000 claims abstract description 29
- 239000001301 oxygen Substances 0.000 claims abstract description 28
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052786 argon Inorganic materials 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 18
- 230000001590 oxidative effect Effects 0.000 claims abstract description 16
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- 230000000630 rising effect Effects 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 claims description 2
- 238000007664 blowing Methods 0.000 claims description 2
- 238000007667 floating Methods 0.000 claims description 2
- 239000010408 film Substances 0.000 claims 6
- 239000010409 thin film Substances 0.000 claims 1
- 238000010924 continuous production Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 description 13
- 238000006460 hydrolysis reaction Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000007062 hydrolysis Effects 0.000 description 10
- 239000012535 impurity Substances 0.000 description 9
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 229960001231 choline Drugs 0.000 description 6
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 6
- 239000010980 sapphire Substances 0.000 description 6
- 229910052594 sapphire Inorganic materials 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000000197 pyrolysis Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- HSEYYGFJBLWFGD-UHFFFAOYSA-N 4-methylsulfanyl-2-[(2-methylsulfanylpyridine-3-carbonyl)amino]butanoic acid Chemical compound CSCCC(C(O)=O)NC(=O)C1=CC=CN=C1SC HSEYYGFJBLWFGD-UHFFFAOYSA-N 0.000 description 4
- -1 Aluminium alkoxide Chemical class 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000010432 diamond Substances 0.000 description 4
- 229910003460 diamond Inorganic materials 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 230000036632 reaction speed Effects 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 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 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000019743 Choline chloride Nutrition 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- LCQXXBOSCBRNNT-UHFFFAOYSA-K ammonium aluminium sulfate Chemical compound [NH4+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCQXXBOSCBRNNT-UHFFFAOYSA-K 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229960003178 choline chloride Drugs 0.000 description 1
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 1
- 230000001713 cholinergic effect Effects 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010437 gem Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GALOTNBSUVEISR-UHFFFAOYSA-N molybdenum;silicon Chemical compound [Mo]#[Si] GALOTNBSUVEISR-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000012609 strong anion exchange resin Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- C01F7/42—Preparation of aluminium oxide or hydroxide from metallic aluminium, e.g. by oxidation
- C01F7/422—Preparation of aluminium oxide or hydroxide from metallic aluminium, e.g. by oxidation by oxidation with a gaseous oxidator at a high temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/0073—Degasification of liquids by a method not covered by groups B01D19/0005 - B01D19/0042
- B01D19/0078—Degasification of liquids by a method not covered by groups B01D19/0005 - B01D19/0042 by vibration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Thermal Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion 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 invention provides a device for preparing high-purity alumina micropowder by directly oxidizing liquid aluminum, which comprises an aluminum melting furnace and an oxidizing furnace, wherein the aluminum melting furnace is used for melting an aluminum source to obtain a height Wen Yelv, and the height Wen Yelv is input into the oxidizing furnace through a pipeline; the liquid aluminum feeding port and the alumina powder pneumatic output port are arranged above the oxidation furnace, the liquid aluminum feeding port is connected with the aluminum melting furnace, an oxygen-argon gas mixture inlet is arranged below the oxidation furnace and used for introducing mixed gas and forming bubbles in liquid aluminum, and an alumina film formed by reacting oxygen in the mixed gas with the liquid aluminum is arranged around the bubbles. The invention makes oxygen in the mixed gas react with liquid aluminum in high temperature liquid aluminum to prepare aluminum oxide powder. And the nano-scale alumina powder is obtained by adopting bubble breaking, and the alumina powder is pneumatically conveyed out by argon. Compared with the prior art, the method has the advantages of simple process, short flow, high purity (4N-6N) of the synthesized alumina micro powder, uniform particle size of the nano-scale powder, and high industrial and continuous production yield.
Description
Technical Field
The invention belongs to the field of inorganic compounds, relates to a preparation device and a preparation method of alumina micropowder, and in particular relates to a device and a method for preparing high-purity alumina micropowder by adopting liquid aluminum direct oxidation.
Background
Alumina is a white crystalline powder, commonly referred to as high purity alumina above 3N (99.9% purity), including 4N (99.99% purity) and 5N (99.999% purity). The high-purity alumina has the characteristics of good sintering property, good dispersion property, porosity and the like, has good mechanical property, thermal property and chemical property, and is widely applied to the fields of LED industry, rare earth trichromatic fluorescent powder, fine ceramics, manufacturing sapphire crystals, lithium battery ceramic diaphragms, integrated circuits, catalyst carriers and the like. With the rapid development of high and new technology industries such as 5G communication, rail transit, aerospace and military industry, the average annual demand growth rate of high-purity alumina worldwide is expected to exceed 20%.
At present, the methods for preparing high-purity aluminum oxide powder in industrialization mainly comprise an aluminum choline oxide hydrolysis method, an aluminum isopropoxide hydrolysis method and an aluminum ammonium sulfate pyrolysis method. The hydrolysis method of the choline aluminum is a main production method of 4N powder (purity 99.99%), the method needs to process the aluminum into sheets or powder, impurities are easy to bring in, the finished product cannot be purified, and the purity of the product can only reach 4N (99.99%). The aluminum isopropoxide hydrolysis method is to prepare high-purity superfine alumina powder by the processes of synthesizing, purifying, hydrolyzing, roasting and the like of aluminum and isopropanol by adding a catalyst, and is a main production method of the existing 5N powder (purity is 99.999%), the purity of the method is strong in controllability, the particle size is small, however, the method is used for alcohol, the production process needs high temperature and high pressure, and the production cost is highHigh and long process. The pyrolysis method of aluminum ammonium sulfate has long production period, thermal dissolution phenomenon and SO generated in the decomposition process 2 、NH 3 Serious environmental pollution is caused, and thus the method is being phased out.
The analysis of the prior art described above is as follows:
1. the hydrolysis method of the choline aluminum comprises the following steps: firstly, preparing high-purity aluminum blocks into aluminum foil or powder with the thickness of about 0.1mm by using a cutter, and converting choline chloride into choline by using strong anion exchange resin; then adding a certain amount of aluminum foil into choline solution with the concentration of 0.1-0.2 for reaction. The temperature of the hydrolysis reaction is controlled to be about 80 ℃, the reaction speed is judged according to the escape speed of hydrogen in the reaction process, when the reaction speed is very low or stops, slurry is removed for solid-liquid separation, and refined aluminum is periodically added to circularly carry out the process. The aluminum hydroxide generated by the hydrolysis reaction is subjected to filtration, spray drying and calcination phase inversion to obtain the fine alumina powder. The production of the technology does not have a purification process, aluminum foil is made of aluminum blocks by using a cutter, impurities are easy to bring in, and the purity of the product can only reach 99.99 percent at maximum. The choline method is the current production method of 4N grade alumina with the largest national standard. Only industrial precious stones and low-end sapphires can be made. The main disadvantage of this process is that it is not possible to purify again, what grade the raw material is, what grade the alumina is made of, and it is not possible to surpass the raw material level. In addition, in the hydrolysis process, in order to increase the reaction contact area, the aluminum material needs to be processed into sheets or powder materials, and impurities such as Fe, ti, ni, zr and the like are easily carried in the process. These impurities have a very large impact on the quality of sapphire.
2. Aluminium alkoxide hydrolysis method
The aluminum alkoxide hydrolysis method is to prepare high-purity superfine alumina powder by the processes of synthesizing, purifying, hydrolyzing, roasting and the like by adding a catalyst into aluminum and isopropanol. The purification is further divided into distillation and rectification, the purity of the distillation is lower than that of the rectification, and the method comprises the following steps: firstly adding aluminum sheet into isopropanol to react to generate aluminum isopropoxide, then distilling, rectifying and purifying the aluminum isopropoxide, hydrolyzing to generate hydrated oxide diamond, and heating and decomposing the hydrated oxide diamond to obtain aluminum oxide. The purity of the alumina produced by the method can reach 5N or even 6N. The high-purity alumina used in LED sapphire crystal growth industry in Japanese and United states before the day is mainly produced by adopting the process, and the process is relatively complex and has the main advantages that:
1) The reaction speed of high-purity aluminum and alcohols is high, powder or foil is not needed to be processed, and metal impurities are prevented from being brought in the processing process.
2) The aluminum isopropoxide obtained by the reaction can be rectified to collect high-purity aluminum isopropoxide in a gaseous form, so that metal impurities such as iron, titanium, nickel, diamond, lead, magnesium and the like can be effectively removed. The condensed high-purity aluminum isopropoxide can be purified again to remove free metal impurities such as potassium, sodium, zinc and the like. This is not possible with other processes.
The alumina powder produced by the method has high purity and small particle size, and the process has strong purity controllability on products and can meet the requirement of sapphire crystal growth. However, the process uses alcohol, high temperature and high pressure are needed, and the product cost is high. However, the product produced by the process has high purity, and only the sapphire crystal grown from the alumina with the purity can meet the requirement of the LED substrate. Therefore, manufacturers of high-quality 5N alumina in the world select an aluminum alkoxide method, and Japanese Sumitomo, an enterprise with the largest yield of 5N alumina in the world, is also used by the method.
3. Ammonium aluminum sulfate pyrolysis process
The aluminum ammonium sulfate pyrolysis method is to dissolve aluminum hydroxide with sulfuric acid to prepare aluminum sulfate solution, then add ammonium sulfate to the solution to react with the aluminum sulfate to prepare ammonium bright vanadium, and then recrystallize for multiple times according to the purity requirement to obtain refined ammonium bright vanadium. Then decomposing the obtained refined ammonium bright vanadium at 1250 ℃ to obtain alumina powder.
Although the method has simple process and relatively low cost, the production period is long, the thermal dissolution phenomenon exists, and SO generated in the decomposition process 3 、NH 3 Serious environmental pollution is caused, and thus the method is being phased out.
The method has the defects that metallic iron, nickel, titanium, diamond plasma and halogen elements are difficult to remove, the purity can reach 4N at most, and the method is basically limited; in terms of purity, the defect of the method is large, and large-size sapphire crystals cannot be prepared, so that the high-end requirements cannot be met.
4. The prior published technical method for preparing the high-purity nano alumina micro powder by adopting high-temperature liquid aluminum comprises the following steps:
patent applications CN02114666, CN200710016471, CN201410626394 and CN201510656825 all disclose methods for preparing aluminum hydroxide by atomizing liquid aluminum at high temperature, and preparing aluminum oxide powder by the procedures of filtering, drying, calcining, crushing and the like, wherein the methods are carried out in aqueous solution or can be contacted with water, the interference of sodium, potassium, hydroxyl ions and the like can not be eliminated, the particle size can not be controlled, and the flow is long.
Patent application CN201711056607 discloses a method and a special device for preparing high-purity alumina powder by a high-purity aluminum atomization rapid combustion method, wherein atomized liquid aluminum drops and oxygen are directly reacted to generate the alumina powder, the method needs high-purity aluminum, the cost is high, the particle size of the alumina powder generated by the reaction after atomization cannot be controlled, and the liquid aluminum drops are not completely reacted.
From the above analysis, it is known that in the existing industrial application method, the cholinergic aluminum hydrolysis method needs to process the aluminum material into sheets or powder, impurities are easy to bring in, the finished product cannot be purified, the purity of the product can only reach 4N (99.99%), and the production flow is long. The aluminum isopropoxide hydrolysis method has strong purity controllability and small particle size, but the method uses alcohol, and the production process needs high temperature and high pressure, so that the production cost is high and the flow is long. The production period of the aluminum ammonium sulfate pyrolysis method is long, the thermal dissolution phenomenon exists, and SO is generated in the decomposition process 3 、NH 3 Can cause serious environmental pollution. Therefore, the published method adopting high-temperature liquid aluminum has the problems of long flow, impurity content, high cost, incomplete reaction and the like.
Therefore, a new technology for preparing the high-purity nano alumina micropowder with low cost and short flow is needed to solve the technical problems.
Disclosure of Invention
In order to solve the technical problems, the invention provides a device and a method for preparing high-purity alumina micropowder by directly oxidizing liquid aluminum, which adopt high-temperature liquid aluminum. The technical scheme of the invention is as follows:
the invention provides a device for preparing high-purity alumina micropowder by directly oxidizing liquid aluminum, which comprises an aluminum melting furnace and an oxidizing furnace, wherein,
the aluminum melting furnace is used for melting an aluminum source to obtain a height Wen Yelv, and inputting the height Wen Yelv into the oxidation furnace through a pipeline;
the liquid aluminum feeding port and the alumina powder pneumatic output port are arranged above the oxidation furnace, the liquid aluminum feeding port is connected with the aluminum melting furnace, and an oxygen-argon gas mixture inlet (hereinafter referred to as mixture) inlet is arranged below the oxidation furnace and used for introducing mixture and forming mixture bubbles in the liquid aluminum.
Preferably, a valve is arranged on a connecting pipeline between the liquid aluminum feeding port and the aluminum melting furnace.
Preferably, the bottom of the oxidation furnace is provided with a plurality of mixed gas injection ports, and the mixed gas injection ports are communicated with a mixed gas inlet positioned outside the oxidation furnace.
Preferably, the inside electric stirrer that is equipped with of oxidation furnace, electric stirrer includes puddler and blade, puddler and blade all are located liquid aluminium liquid level below.
The invention also provides a method for preparing high-purity alumina micropowder by using the device for direct oxidation, which comprises the following steps:
1) And (3) putting the aluminum source into an aluminum melting furnace, heating until the aluminum source is completely melted, opening a valve, conveying high-temperature liquid aluminum into an oxidation furnace filled with mixed gas, and closing the valve after the liquid level in the oxidation furnace reaches a specified height.
Preferably, the aluminum source is selected from at least one of industrial aluminum block, industrial aluminum powder, cleaned scrap aluminum, aluminum alloy.
Preferably, the heating temperature of the aluminum melting furnace is 850-1000 ℃.
Preferably, a certain space is reserved above the liquid level of the liquid aluminum in the oxidation furnace.
2) Introducing mixed gas into the oxidation furnace from a mixed gas inlet at the bottom of the oxidation furnace, enabling the mixed gas to enter liquid aluminum through a plurality of mixed gas blowing openings, forming mixed gas bubbles in the liquid aluminum, enabling oxygen in the mixed gas to react with the liquid aluminum in the rising process of the bubbles, and enabling oxygen at the periphery of the bubbles to contact the liquid aluminum for reaction to form a layer of aluminum oxide film.
Preferably, the alumina film thickness is 0.01-0.3 μm.
Preferably, the oxygen content in the mixed gas is 10% -30%, the balance is nitrogen, the purity of the oxygen and the argon is not less than 99.99%, and the supply amount is 10-100L/min.
The temperature in the oxidation furnace is 1000-1300 ℃.
3) When the alumina bubble film in the high-temperature liquid aluminum generates floating, an electric stirrer arranged in the oxidation furnace rotates, the blades break up the rising bubble film to generate nanoscale micro alumina particles which continue to float to the surface of the liquid aluminum, the mixed gas wrapped after breaking the bubble film in the liquid aluminum is released, and oxygen in the mixed gas continuously contacts and reacts with the liquid aluminum to generate the alumina bubble film and alumina powder.
Preferably, the electric stirrer rotates at a speed of 300-1000RPM.
4) The bubbles rise to the liquid aluminum surface and burst, the alumina film breaks into nano-sized powder, and the nano-sized alumina particles generated in the liquid aluminum together with the air flow fly in the space above the liquid aluminum surface.
Preferably, the average particle size of the nanoscale powder is 0.05-0.5 μm.
5) The positive pressure is kept above the liquid level of the liquid aluminum in the oxidation furnace, and the scattered aluminum oxide powder enters the radiator for cooling through the pneumatic output port of the aluminum oxide powder at the top by the pneumatic transmission of argon in the mixed gas.
Preferably, the heat sink region temperature is no higher than 260 ℃.
6) The cooled alumina powder and argon enter a gas-powder separation device, the alumina powder is separated out for powder collection, and the argon enters a mixed gas supply device for recycling.
The particle size of the alumina powder is 0.05-0.5 mu m, and the purity of the alumina is more than 99.99% (4N) or above.
The invention has the following beneficial effects:
the invention adopts oxygen and argon mixed gas to be introduced into high-temperature liquid aluminum to form bubbles, and oxygen in the bubbles reacts with the liquid aluminum to prepare alumina powder. And crushing the bubbles to obtain the nano-scale alumina powder. Compared with the prior art, the method has the advantages of simple process, short flow, high purity (4N-6N) of the synthesized alumina micro powder, uniform particle size of the nano-scale powder, and high industrial and continuous production yield.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a block diagram of an apparatus for preparing high purity alumina micropowder by direct oxidation of liquid aluminum in accordance with the present invention;
wherein, a 1-aluminum melting furnace; 2-high Wen Yelv; 3-valve; a 4-oxidation furnace; a 5-oxygen argon gas mixture inlet; 6-oxygen and argon mixed gas jetting port and 7-electric stirrer; 8-alumina powder pneumatic output port; 9-stirring rod and blade; 10-liquid aluminum feeding port.
Detailed Description
In order to make the objects, technical solutions and advantageous technical effects of the present invention clearer, the present invention will be described in detail with reference to specific embodiments. It should be understood that the examples described in this specification are for the purpose of illustrating the invention only and are not intended to limit the invention.
The embodiment of the invention provides a device for preparing high-purity alumina micropowder by directly oxidizing liquid aluminum, which is shown in figure 1 and comprises an aluminum melting furnace 1 and an oxidizing furnace 4, wherein,
the aluminum melting furnace 1 is used for melting an aluminum source to obtain high-temperature liquid aluminum 2, and inputting the high-temperature liquid aluminum 2 into the oxidizing furnace 4 through a pipeline;
the liquid aluminum feeding port 10 and the alumina powder pneumatic output port 8 are arranged above the oxidation furnace 4, the liquid aluminum feeding port 10 is connected with the aluminum melting furnace 1, the oxygen-argon mixed gas inlet 5 is arranged below the oxidation furnace 4 and is used for introducing mixed gas and forming mixed gas bubbles in the liquid aluminum, and oxygen in the mixed gas around the bubbles contacts the liquid aluminum to react to form a layer of alumina film. When the bubbles rise to the liquid level of the liquid aluminum, the bubbles burst, the alumina film is broken into nano powder, the nano powder enters a space above the liquid aluminum, and the alumina powder is collected through an alumina powder pneumatic output port 8.
In one embodiment of the invention, a valve 3 is arranged on a connecting pipeline of the liquid aluminum feeding port 10 and the aluminum melting furnace 1 and is used for inputting liquid aluminum into the oxidizing furnace 4 in a staged manner.
In one embodiment of the present invention, a plurality of oxygen-argon gas mixture injection nozzles 6 are arranged at the bottom of the oxidation furnace 4, and the mixture injection nozzles 6 are communicated with a mixture inlet 5 positioned outside the oxidation furnace 4 and are used for forming fine mixture bubbles in liquid aluminum, so that the contact area between the bubbles and the liquid aluminum is increased.
In one embodiment of the invention, an electric stirrer 7 is arranged inside the oxidation furnace 4, the electric stirrer 7 comprises stirring rods and blades 9, and the stirring rods and the blades 9 are positioned below the liquid level of the liquid aluminum and are used for breaking up the rising mixed gas bubble film and increasing the gas-liquid reaction times.
The invention also provides a method for preparing high-purity alumina micropowder by using the device for direct oxidation, which comprises the following steps:
1) The aluminum source is put into an aluminum melting furnace 1, after the aluminum source is heated to be completely melted, a valve 3 is opened to convey high-temperature liquid aluminum 2 into an oxidation furnace 4 filled with mixed gas, and after the liquid level in the oxidation furnace 4 reaches a specified height, the valve 3 is closed.
In one embodiment of the present invention, the aluminum source is selected from at least one of an industrial aluminum block, an industrial aluminum powder, a cleaned scrap aluminum, an aluminum alloy.
In one embodiment of the invention, the heating temperature of the aluminum melting furnace 1 is 850-1000 ℃, and high-temperature liquid aluminum 2 is obtained in the aluminum melting furnace 1 at the temperature, and the temperature of the high-temperature liquid aluminum 2 is the same as the heating temperature of the aluminum melting furnace 1. The heating method of the aluminum melting furnace 1 is not limited to electric furnace heating, arc heating, silicon-molybdenum rod heating, or the like.
In one embodiment of the invention, a certain space is reserved above the liquid level of the liquid aluminum in the oxidation furnace 4 for the alumina powder to escape after the alumina bubbles are broken. Preferably, this space occupies 1/4 of the volume inside the oxidation oven 4.
2) Introducing mixed gas into the oxidation furnace 4 from an oxygen-argon mixed gas inlet 5 at the bottom of the oxidation furnace 4, enabling the mixed gas to enter liquid aluminum through a plurality of oxygen-argon mixed gas injection openings 6, forming mixed gas bubbles in the liquid aluminum, enabling oxygen in the mixed gas to react with the liquid aluminum in the rising process of the bubbles, and enabling oxygen at the periphery of the bubbles to contact with the liquid aluminum to react to form a layer of aluminum oxide film.
In one embodiment of the invention, the alumina film thickness is 0.01-0.3 μm.
In one embodiment of the invention, the oxygen content in the mixed gas is 10-30% (volume), the balance is argon, the purity of the oxygen and the argon is not less than 99.99%, and the supply amount is 10-100L/min. The applicant researches find that if the oxygen content in the introduced pure oxygen or the mixed gas is too high, potential safety hazards exist. The oxygen in the mixed gas is kept in the content range, so that the oxygen in the mixed gas can be fully reacted, and the basic argon overflowed after the bubble is broken can be avoided, and the excessive oxygen pressure in the oxidation furnace 4 is avoided.
In one embodiment of the invention, the temperature in the oxidizing furnace 4 is 1000-1300 ℃. If the temperature in the oxidizing furnace 4 is too low, the reaction speed is low, and the efficiency of generating alumina is low; if the temperature is too high, the reaction is not easy to control, and the aluminum liquid is easy to volatilize.
The reaction formula of the step is as follows: 4al+3o2=2al 2 O 3 The adding amount of liquid aluminum in the oxidation furnace 4 is far larger than the introducing amount of oxygen in the mixed gas, namely, the excessive liquid aluminum is ensured, so that the reaction is continuously carried out.
3) When the alumina bubble film in the high-temperature liquid aluminum generates and floats upwards, the electric stirrer 7 arranged in the oxidation furnace 4 rotates, the stirring rod and the blades 9 break up the rising bubble film, and nano-scale micro alumina particles are generated and continuously float upwards to the surface of the liquid aluminum. And the mixed gas wrapped after the bubble film in the liquid aluminum is broken is released, and oxygen in the mixed gas continuously contacts and reacts with the liquid aluminum to generate an alumina bubble film and alumina powder.
In one embodiment of the invention, the electric stirrer 7 is rotated at 300-1000RPM. The stirring rod and the blades of the electric stirrer can be made of graphite, corundum and other high-temperature resistant materials.
4) The bubbles rise to the liquid aluminum surface and burst, the alumina film breaks into nano-sized powder, and the nano-sized alumina particles generated in the liquid aluminum together with the air flow fly in the space above the liquid aluminum surface.
In one embodiment of the invention, the nanoscale powder has an average particle size of 0.05-0.5 μm.
5) The positive pressure is kept above the liquid level of the liquid aluminum in the oxidation furnace 4, and the scattered aluminum oxide powder is conveyed into a radiator (not shown in the figure) by argon gas in the mixed gas through an aluminum oxide powder pneumatic output port 8 at the top end for cooling.
In one embodiment of the invention, the temperature of the radiator area is not higher than 260 ℃ in consideration of the fact that the temperature resistance of the cloth bag powder collector which is used later is 150-260 ℃. The cooling mode of the radiator is not limited to air cooling, liquid cooling and the like.
6) The cooled alumina powder and argon enter a gas-powder separation device, the alumina powder is separated out for powder collection, and the argon enters a mixed gas supply device for recycling.
The particle size of the alumina powder is 0.05-0.5 mu m, and the purity of the alumina is more than 99.99% (4N) or above.
The above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto. Various equivalent modifications and substitutions will occur to those skilled in the art, and these are intended to be included within the scope of the present invention. Therefore, the protection scope of the invention is subject to the protection scope defined by the claims.
Claims (10)
1. The device for preparing high-purity alumina micropowder by directly oxidizing liquid aluminum is characterized by comprising an aluminum melting furnace and an oxidizing furnace, wherein,
the aluminum melting furnace is used for melting an aluminum source to obtain a height Wen Yelv, and inputting the height Wen Yelv into the oxidation furnace through a pipeline;
the liquid aluminum feeding port and the alumina powder pneumatic output port are arranged above the oxidation furnace, the liquid aluminum feeding port is connected with the aluminum melting furnace, and an oxygen-argon gas mixture inlet is arranged below the oxidation furnace and used for introducing mixture gas and forming bubbles in the liquid aluminum.
2. The device for preparing high-purity alumina micropowder by direct oxidation of liquid aluminum according to claim 1, wherein a valve is arranged on a connecting pipeline between the liquid aluminum feeding port and the aluminum melting furnace.
3. The apparatus for preparing high-purity alumina fine powder by direct oxidation of liquid aluminum according to claim 2, wherein the bottom of the oxidation furnace is provided with a plurality of mixed gas injection ports, and the mixed gas injection ports are communicated with a mixed gas inlet positioned outside the oxidation furnace.
4. The device for preparing high-purity alumina micro powder by directly oxidizing liquid aluminum according to claim 3, wherein an electric stirrer is arranged in the oxidizing furnace and comprises stirring rods and blades, and the stirring rods and the blades are all positioned below the liquid aluminum liquid surface.
5. A method for preparing high-purity alumina fine powder by direct oxidation using the apparatus according to any one of claims 1 to 4, comprising the steps of:
1) Putting an aluminum source into an aluminum melting furnace, heating until the aluminum source is completely melted, opening a valve, conveying high-temperature liquid aluminum into an oxidation furnace filled with mixed gas, and closing the valve after the liquid level in the oxidation furnace reaches a specified height;
2) Introducing mixed gas into the oxidation furnace from a mixed gas inlet at the bottom of the oxidation furnace, enabling the mixed gas to enter liquid aluminum through a plurality of mixed gas blowing openings, forming mixed gas bubbles in the liquid aluminum, enabling oxygen in the mixed gas to react with the liquid aluminum in the rising process of the bubbles, and enabling oxygen at the periphery of the bubbles to contact the liquid aluminum to react to form a layer of aluminum oxide film;
3) When the alumina bubble film in the high-temperature liquid aluminum generates upward floating, an electric stirrer arranged in the oxidation furnace rotates, the blades break up the rising bubble film to generate nanoscale micro alumina particles which continue to float to the surface of the liquid aluminum, the mixed gas wrapped after breaking the bubble film in the liquid aluminum is released, and oxygen in the mixed gas continuously contacts with the liquid aluminum to react to generate the alumina bubble film and alumina powder;
4) The bubbles rise to the liquid aluminum surface and burst, the alumina film is broken into nano-scale powder, and the nano-scale alumina particles generated in the liquid aluminum together with the air flow float in the space above the liquid aluminum surface;
5) The positive pressure is kept above the liquid level of the liquid aluminum in the oxidation furnace, and the scattered aluminum oxide powder enters a radiator for cooling through the pneumatic output port of the aluminum oxide powder at the top by the pneumatic transmission of argon in the mixed gas;
6) The cooled alumina powder and argon enter a gas-powder separation device, the alumina powder is separated out for powder collection, and the argon enters a mixed gas supply device for recycling.
6. The method according to claim 5, wherein in step 1), the heating temperature of the aluminum melting furnace is 850-1000 ℃; and/or
A certain space is reserved above the liquid level of the liquid aluminum in the oxidation furnace, and the space occupies 1/4 of the volume in the oxidation furnace.
7. The method according to claim 5, wherein in step 2), the alumina thin film has a thickness of 0.01 to 0.3 μm; and/or
The oxygen content in the mixed gas is 10% -30%, the balance is argon, the purity of the oxygen and the argon is not less than 99.99%, and the supply amount is 10-100L/min; and/or
The temperature in the oxidation furnace is 1000-1300 ℃.
8. The method of claim 5, wherein in step 3), the electric stirrer is rotated at 300-1000RPM.
9. The method of claim 5, wherein in step 5), the heat sink region temperature is no greater than 260 ℃.
10. The method according to claim 5, wherein in step 6), the alumina powder has a particle size of 0.05 to 0.5 μm and an alumina purity of more than 99.99% or more.
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