CN110577758A - Method for preparing carbon anode antioxidant coating for electrolytic aluminum by comprehensively utilizing aluminum ash - Google Patents
Method for preparing carbon anode antioxidant coating for electrolytic aluminum by comprehensively utilizing aluminum ash Download PDFInfo
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- CN110577758A CN110577758A CN201910875417.5A CN201910875417A CN110577758A CN 110577758 A CN110577758 A CN 110577758A CN 201910875417 A CN201910875417 A CN 201910875417A CN 110577758 A CN110577758 A CN 110577758A
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- aluminum
- carbon anode
- aluminum ash
- ash
- electrolytic
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 202
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 187
- 238000000034 method Methods 0.000 title claims abstract description 71
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 66
- 238000000576 coating method Methods 0.000 title claims abstract description 54
- 239000011248 coating agent Substances 0.000 title claims abstract description 53
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 12
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003513 alkali Substances 0.000 claims abstract description 25
- 239000000945 filler Substances 0.000 claims abstract description 24
- 239000000853 adhesive Substances 0.000 claims abstract description 23
- 230000001070 adhesive effect Effects 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002585 base Substances 0.000 claims abstract description 17
- 238000001704 evaporation Methods 0.000 claims abstract description 16
- 230000008020 evaporation Effects 0.000 claims abstract description 16
- 239000000706 filtrate Substances 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000012153 distilled water Substances 0.000 claims abstract description 15
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 13
- 150000001639 boron compounds Chemical class 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000011344 liquid material Substances 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 14
- 238000005868 electrolysis reaction Methods 0.000 claims description 12
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 11
- 229910021538 borax Inorganic materials 0.000 claims description 11
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 11
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 11
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 11
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 7
- 229910052580 B4C Inorganic materials 0.000 claims description 4
- 239000004375 Dextrin Substances 0.000 claims description 4
- 229920001353 Dextrin Polymers 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 4
- 235000019425 dextrin Nutrition 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 230000008929 regeneration Effects 0.000 claims description 4
- 238000011069 regeneration method Methods 0.000 claims description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 6
- 230000003064 anti-oxidating effect Effects 0.000 abstract description 3
- 239000002910 solid waste Substances 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract 1
- 239000002699 waste material Substances 0.000 description 9
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- 239000002893 slag Substances 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 7
- 239000010405 anode material Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 4
- 239000002440 industrial waste Substances 0.000 description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- CAVCGVPGBKGDTG-UHFFFAOYSA-N alumanylidynemethyl(alumanylidynemethylalumanylidenemethylidene)alumane Chemical compound [Al]#C[Al]=C=[Al]C#[Al] CAVCGVPGBKGDTG-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000004673 fluoride salts Chemical class 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910021364 Al-Si alloy Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
- C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
- C25C3/12—Anodes
- C25C3/125—Anodes based on carbon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention provides a method for preparing carbon anode antioxidant coating for electrolytic aluminum by comprehensively utilizing aluminum ash; the raw materials comprise aluminum ash, strong base, aluminum powder, boron compound, organic adhesion promoter and water in parts by weight; the preparation method comprises the following steps: adding aluminum ash into water, and keeping the temperature under the stirring condition; collecting the generated ammonia gas, cooling the liquid material, filtering, transferring the filtrate into evaporation equipment to evaporate and recover soluble chloride in the filtrate, and collecting distilled water generated in the evaporation process; adding a strong base to the solution to obtain an alkali solution; adding filter residue and aluminum powder obtained by filtering, stirring, and obtaining carbon anode coating adhesive and filler for electrolytic aluminum after partial alkali dissolution; finally, adding a boron compound and an organic adhesion promoter into the adhesive, and uniformly mixing; the invention prepares the carbon anode antioxidant coating for electrolytic aluminum by taking solid waste aluminum ash as a raw material, not only can comprehensively recycle the aluminum ash, but also can ensure that the prepared coating can ensure that the carbon anode for electrolytic aluminum has high-temperature resistance and antioxidation.
Description
Technical Field
The invention belongs to the technical field of comprehensive utilization and treatment of solid wastes, and particularly relates to a method for preparing a carbon anode antioxidant coating for electrolytic aluminum by comprehensively utilizing aluminum ash.
Background
The aluminum ash is mainly derived from the links of aluminum production, consumption, waste aluminum regeneration and the like. The aluminum ash produced during aluminum smelting is industrial waste residue with large yield and serious pollution. Aluminum ash is produced during the production of fused salt electrolysis of aluminum oxide, and a certain amount of aluminum ash is also produced due to the carrying of operating and measuring instruments, anode replacement, aluminum discharge, ingot casting and electrolytic bath overhaul. The aluminum ash and aluminum slag just discharged from the furnace contains a large amount of metal aluminum, wherein only part of aluminum can be recovered, and the rest aluminum ash is accumulated in a factory or buried, so that not only is the resource waste caused, but also the environmental pollution is brought. According to statistics, 25-50 kg of aluminum ash is generated when 1000 kg of aluminum is produced in China, and the yield of electrolytic aluminum in 2018 in China is about 3,649 ten thousand tons, so that about 900 ten thousand tons of aluminum ash are generated in 2018 in China. At present, the residual ash after the recovery of the metal aluminum can be used for producing aluminum oxide, preparing a water purifying agent, synthesizing or preparing an Al-Si alloy, synthesizing a refractory material, a steelmaking deoxidizer and a road building material in a semi-rigid base layer, but more residual waste aluminum ash can still not be utilized. The waste aluminum ash is stored in an aluminum ash storage yard, which not only occupies the field, but also easily causes water and soil pollution. The production and living are seriously influenced by the stockpiling of the waste aluminum ash, so that a method for increasing the comprehensive recycling of the aluminum ash is urgent.
Disclosure of Invention
in order to solve the above-mentioned purpose, the invention provides a method for preparing carbon anode antioxidant coating for electrolytic aluminum by comprehensively utilizing aluminum ash. The coating is prepared by taking solid waste-aluminum ash as a raw material, so that the aluminum ash can be comprehensively recycled, and the prepared coating can enable the carbon anode for electrolytic aluminum to have high-temperature resistance and antioxidation.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing carbon anode oxidation resistant coating for electrolytic aluminum by comprehensively utilizing aluminum ash comprises the following raw materials in parts by weight: 20-70 parts of aluminum ash, 5-30 parts of strong base, 1-10 parts of aluminum powder, 1-20 parts of boron compound, 0.5-3 parts of organic adhesion promoter and 5-50 parts of water.
As a further improvement of the invention, the aluminum ash is aluminum ash generated in at least one process of aluminum casting, aluminum regeneration and aluminum electrolysis. The aluminum ash is obtained by grinding and sieving aluminum ash slag; the particle size is preferably 100-200 meshes; the aluminum ash comprises the following chemical components: metal aluminum, fluoride salt, chloride salt, alumina, aluminum nitride, aluminum carbide, and oxides of metals such as silicon, iron, magnesium, manganese, zinc, and copper.
As a further improvement of the invention, the organic adhesion promoter is at least one of carboxymethyl cellulose, polyvinyl alcohol and dextrin.
as a further improvement of the invention, the strong base is at least one of sodium hydroxide and potassium hydroxide.
As a further improvement of the invention, the boron compound is at least one of sodium borate and boron carbide.
A method for preparing carbon anode oxidation resistant coating for electrolytic aluminum by comprehensively utilizing aluminum ash comprises the following steps:
1) accurately weighing the raw materials according to the proportion;
2) Adding aluminum ash into water, stirring, and keeping the temperature at 50-120 ℃ until no ammonia gas is generated; during which ammonia gas is collected; the step is a water leaching process of aluminum ash, and mainly aims to convert aluminum nitride into aluminum oxide;
3) Cooling the liquid material generated in the step 2) to room temperature, filtering, transferring the filtrate into evaporation equipment to evaporate and recover soluble chloride in the filtrate, and collecting distilled water generated in the evaporation process;
4) Adding strong base into distilled water to obtain an alkali solution;
5) adding the filter residue obtained by filtering in the step 3) into an alkali solution, adding aluminum powder, uniformly stirring, and stirring for 5-150 minutes at the temperature of room temperature-150 ℃, wherein the aluminum ash is partially alkali-dissolved in the process, and the alkali-dissolved part directly becomes a coating adhesive; the part of the aluminum ash which is not dissolved by alkali becomes a filler; namely, the product obtained in the process is a mixture of the adhesive and the filler;
6) adding boron compound and organic adhesion promoter into the mixture of the adhesive and the filler, and uniformly mixing to obtain the carbon anode coating for electrolytic aluminum.
As a further improvement of the invention, the heat preservation time in the step 1) is 1-10 hours.
As a further improvement of the invention, the ammonia gas collecting method comprises the following steps: and introducing ammonia gas into water for collection.
The invention has the following technical effects:
the carbon anode coating for electrolytic aluminum prepared by the invention has good high temperature resistance and oxidation resistance, and the aluminum electrolysis process is a molten salt electrolysis process with a carbon material as an anode. However, the anode material is seriously consumed in the process of electrolyzing the aluminum, which not only influences the product purity of the electrolytic aluminum, but also increases the economic cost for enterprises. The threshing, chipping and oxidation burning of the anode in the using process are main causes of the increase of the consumption of carbon materials. The anode oxidation combustion loss is carbon consumption caused by oxidation reaction of high-temperature carbon with oxygen and carbon dioxide in air because the carbon block is exposed in the atmospheric environment. The aluminum electrolysis temperature is about 960 ℃, and during the aluminum electrolysis production, because the anode carbon material is directly exposed in the atmospheric environment, the high-temperature carbon material is in contact with oxygen in the air, oxidized and combusted, the idle consumption of the carbon material is caused, and the idle consumption of the carbon material is an important reason for influencing the consumption of the carbon material to be higher than the theoretical consumption. The carbon anode material for electrolytic aluminum prepared by the method can resist high temperature of more than 1200 ℃, and the carbon anode material is coated on the outer surface of the carbon anode material for electrolytic aluminum, so that the electrolytic efficiency and performance of the carbon anode material are not affected, the high-temperature-resistant and anti-oxidation effect of the carbon anode material is increased, and the carbon consumption in the electrolytic aluminum process is greatly reduced.
the invention takes the industrial waste aluminum ash as the raw material, the aluminum ash reacts with strong base to partially dissolve in alkali, the alkali-dissolved part of the aluminum ash can directly become the adhesive of the coating, and the part of the aluminum ash which is not dissolved in alkali becomes the filler of the coating. Because no additional adhesive, alumina and other fillers are needed, the steps of paint production can be simplified and the cost can be greatly saved. In addition, the preparation process of the invention is collected in the whole process, and no waste water, waste gas or waste residue is discharged. As the electrolytic aluminum process needs fluorine element, the carbon anode oxidation resistant coating for electrolytic aluminum prepared by comprehensively utilizing aluminum ash does not need a special fluorine removal process, thereby greatly reducing the difficulty in the comprehensive utilization process of the aluminum ash.
The method takes the industrial waste aluminum ash as the raw material, does not need to apply complex pretreatment processes such as impurity removal and purification, directly applies the industrial waste aluminum ash as the raw material to the preparation of the electrolytic aluminum carbon anode coating, does not generate secondary waste in the whole process of preparing the coating subsequently, realizes the complete utilization of the aluminum ash, can recycle the waste such as the aluminum ash and the like by large-scale popularization, solves the problem of aluminum ash storage yard, realizes the utilization of the waste, and improves the development and utilization value of the aluminum ash.
Drawings
in order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a process flow diagram of the preparation method of the present invention.
Detailed Description
reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
it will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
A method for preparing carbon anode oxidation resistant coating for electrolytic aluminum by comprehensively utilizing aluminum ash comprises the following raw materials in parts by weight: 20-70 parts of aluminum ash, 5-30 parts of strong base, 1-10 parts of aluminum powder, 1-20 parts of boron compound, 0.5-3 parts of organic adhesion promoter and 5-50 parts of water.
as a preferred embodiment of the present invention, the aluminum ash is aluminum ash generated during at least one process of aluminum casting, aluminum regeneration and aluminum electrolysis. The aluminum ash is obtained by grinding and sieving aluminum ash slag; the particle size is preferably 100-200 meshes; the aluminum ash comprises the following chemical components: metal aluminum, fluoride salt, chloride salt, alumina, aluminum nitride, aluminum carbide, and oxides of metals such as silicon, iron, magnesium, manganese, zinc, and copper.
As a preferred embodiment of the present invention, the organic adhesion promoter is at least one of carboxymethyl cellulose, polyvinyl alcohol, and dextrin.
As a preferred embodiment of the present invention, the strong base is at least one of sodium hydroxide and potassium hydroxide.
in a preferred embodiment of the present invention, the boron compound is at least one of sodium borate and boron carbide.
A method for preparing carbon anode oxidation resistant coating for electrolytic aluminum by comprehensively utilizing aluminum ash comprises the following steps:
1) accurately weighing the raw materials according to the proportion;
2) adding aluminum ash into water, stirring, and keeping the temperature at 50-120 ℃ until no ammonia gas is generated; during which ammonia gas is collected; the step is a water leaching process of aluminum ash, and mainly aims to convert aluminum nitride into aluminum oxide;
3) Cooling the liquid material generated in the step 2) to room temperature, filtering, transferring the filtrate into evaporation equipment to evaporate and recover soluble chloride in the filtrate, and collecting distilled water generated in the evaporation process;
4) Adding strong base into distilled water to obtain an alkali solution;
5) adding the filter residue obtained by filtering in the step 3) into an alkali solution, adding aluminum powder, uniformly stirring, and stirring for 5-150 minutes at the temperature of room temperature-150 ℃, wherein the aluminum ash is partially alkali-dissolved in the process, and the alkali-dissolved part directly becomes a coating adhesive; the part of the aluminum ash which is not dissolved by alkali becomes a filler; namely, the product obtained in the process is a mixture of the adhesive and the filler;
6) Adding boron compound and organic adhesion promoter into the mixture of the adhesive and the filler, and uniformly mixing to obtain the carbon anode coating for electrolytic aluminum.
7) and uniformly mixing to obtain the carbon anode coating for electrolytic aluminum.
As a preferred embodiment of the invention, the heat preservation time in the step 1) is 1-10 hours.
As a preferred embodiment of the present invention, the ammonia gas collecting method comprises: and introducing ammonia gas into water for collection.
The technical solution of the present invention will be described in further detail below with reference to specific examples.
In the following examples, the aluminum ash is derived from aluminum ash slag generated in an electrolytic aluminum plant in Binzhou, Shandong province, and the main components of the aluminum ash are shown in Table 1 after analysis;
TABLE 1 aluminum ash principal Components
example 1: carbon anode coating for preparing electrolytic aluminum
1) Accurately weighing the following raw materials in proportion:
20 parts of aluminum ash, 5 parts of sodium hydroxide, 1 part of industrial aluminum powder, 1 part of sodium borate, 1 part of carboxymethyl cellulose and 15 parts of water, which are generated in the aluminum electrolysis process; wherein the aluminum ash is derived from aluminum ash slag generated by an electrolytic aluminum factory in Binzhou city, Shandong province, and is obtained by grinding and sieving with a 200-mesh sieve;
2) adding aluminum ash into water, stirring, and keeping the temperature at 75 ℃ for 3h until no ammonia gas is generated; during which ammonia gas is collected; the step is a water leaching process of aluminum ash, and mainly aims to convert aluminum nitride into aluminum oxide;
3) Cooling the liquid material generated in the step 2) to room temperature, filtering, transferring the filtrate into evaporation equipment to evaporate and recover soluble chloride in the filtrate, and collecting distilled water generated in the evaporation process;
4) Adding strong base into distilled water to obtain an alkali solution;
5) Adding the filter residue obtained by filtering in the step 3) into an alkali solution, adding aluminum powder, uniformly stirring, and stirring at room temperature for 20 minutes, wherein the aluminum ash is partially alkali-dissolved in the process, and the alkali-dissolved part directly becomes a coating adhesive; the part of the aluminum ash which is not dissolved by alkali becomes a filler; namely, the product obtained in the process is a mixture of the adhesive and the filler;
6) adding sodium borate and carboxymethyl cellulose into the mixture of the adhesive and the filler, and uniformly mixing to obtain the carbon anode coating for electrolytic aluminum.
example 2: carbon anode coating for preparing electrolytic aluminum
1) Accurately weighing the following raw materials in proportion:
50 parts of aluminum ash, 10 parts of sodium hydroxide, 3 parts of industrial aluminum powder, 2 parts of sodium borate, 1 part of carboxymethyl cellulose and 15 parts of water, which are generated in the aluminum electrolysis process; wherein the aluminum ash is derived from aluminum ash slag generated by an electrolytic aluminum factory in Binzhou city, Shandong province, and is obtained by grinding and sieving with a 200-mesh sieve;
2) Adding aluminum ash into water, stirring, and keeping the temperature at 100 ℃ for 5 hours until no ammonia gas is generated; during which ammonia gas is collected; the step is a water leaching process of aluminum ash, and mainly aims to convert aluminum nitride into aluminum oxide;
3) Cooling the liquid material generated in the step 2) to room temperature, filtering, transferring the filtrate into evaporation equipment to evaporate and recover soluble chloride in the filtrate, and collecting distilled water generated in the evaporation process;
4) adding strong base into distilled water to obtain an alkali solution;
5) Adding the filter residue obtained by filtering in the step 3) into an alkali solution, adding aluminum powder, uniformly stirring, and stirring at room temperature for 30 minutes, wherein the aluminum ash is partially alkali-dissolved in the process, and the alkali-dissolved part directly becomes a coating adhesive; the part of the aluminum ash which is not dissolved by alkali becomes a filler; namely, the product obtained in the process is a mixture of the adhesive and the filler;
6) adding sodium borate and carboxymethyl cellulose into the mixture of the adhesive and the filler, and uniformly mixing to obtain the carbon anode coating for electrolytic aluminum.
example 3: carbon anode coating for preparing electrolytic aluminum
1) accurately weighing the following raw materials in proportion:
45 parts of aluminum ash, 15 parts of sodium hydroxide, 5 parts of industrial aluminum powder, 1 part of sodium borate, 3 parts of carboxymethyl cellulose and 50 parts of water, which are generated in the aluminum electrolysis process; wherein the aluminum ash is derived from aluminum ash slag generated by an electrolytic aluminum factory in Binzhou city, Shandong province, and is obtained by grinding and sieving with a 200-mesh sieve;
2) adding aluminum ash into water, stirring, and keeping the temperature at 80 ℃ for 10 hours until no ammonia gas is generated; during which ammonia gas is collected; the step is a water leaching process of aluminum ash, and mainly aims to convert aluminum nitride into aluminum oxide;
3) Cooling the liquid material generated in the step 2) to room temperature, filtering, transferring the filtrate into evaporation equipment to evaporate and recover soluble chloride in the filtrate, and collecting distilled water generated in the evaporation process;
4) Adding strong base into distilled water to obtain an alkali solution;
5) Adding the filter residue obtained by filtering in the step 3) into the alkali solution, adding aluminum powder, stirring uniformly, stirring for 30 minutes at room temperature, and enabling the part of the aluminum ash which is not dissolved in the alkali to become a filler; namely, the product obtained in the process is a mixture of the adhesive and the filler;
6) Adding sodium borate and carboxymethyl cellulose into the mixture of the adhesive and the filler, and uniformly mixing to obtain the carbon anode coating for electrolytic aluminum.
Example 4: carbon anode coating for preparing electrolytic aluminum
1) Accurately weighing the following raw materials in proportion:
70 parts of aluminum ash, 20 parts of sodium hydroxide, 10 parts of industrial aluminum powder, 2 parts of sodium borate, 3 parts of carboxymethyl cellulose and 50 parts of water, which are generated in the aluminum electrolysis process; wherein the aluminum ash is derived from aluminum ash slag generated by an electrolytic aluminum factory in Binzhou city, Shandong province, and is obtained by grinding and sieving with a 200-mesh sieve;
2) adding aluminum ash into water, stirring, and keeping the temperature at 120 ℃ for 6h until no ammonia gas is generated; during which ammonia gas is collected; the step is a water leaching process of aluminum ash, and mainly aims to convert aluminum nitride into aluminum oxide;
3) Cooling the liquid material generated in the step 2) to room temperature, filtering, transferring the filtrate into evaporation equipment to evaporate and recover soluble chloride in the filtrate, and collecting distilled water generated in the evaporation process;
4) Adding strong base into distilled water to obtain an alkali solution;
5) Adding the filter residue obtained by filtering in the step 3) into the alkali solution, adding aluminum powder, stirring uniformly, stirring for 150 minutes at room temperature, and enabling the part of aluminum ash which is not dissolved in the alkali to become a filler; namely, the product obtained in the process is a mixture of the adhesive and the filler;
6) Adding sodium borate and carboxymethyl cellulose into the mixture of the adhesive and the filler, and uniformly mixing to obtain the carbon anode coating for electrolytic aluminum.
example 5: carbon anode coating for preparing electrolytic aluminum
the difference between this example and example 3 is that dextrin is used as the adhesion promoter, and the rest of the steps and parameters are the same as those of example 3, so as to prepare the carbon anode coating for electrolytic aluminum.
example 6: preparation of carbon anode coating for electrolytic aluminum this example differs from example 3 only in that the boron compound is boron carbide, and the rest of the steps and parameters are the same as those of example 3, to prepare the carbon anode coating for electrolytic aluminum.
Example 7: carbon anode coating for preparing electrolytic aluminum
this example is different from example 3 only in that the adhesion promoter is polyvinyl alcohol, and the rest of the steps and parameters are the same as those of example 3, so as to prepare the carbon anode coating for electrolytic aluminum.
example 8: preparation of carbon anode electrode material
Directly coating the coating prepared in the embodiment 1-7 on the surface of a carbon anode for electrolytic aluminum, wherein the thickness of the coating is 0.5-0.7 mm; and drying in the shade for 5h, after primary curing, electrifying the carbon anode for electrolytic aluminum for 1.5-2h, raising the temperature, further hardening the coating, and forming a compact protective coating on the surface of the carbon anode for electrolytic aluminum to form the high-temperature-resistant antioxidant carbon anode. For convenience of description, carbon anodes formed by applying the coatings prepared in examples 1 to 8 to the surface of a carbon anode for electrolytic aluminum were named carbon anodes 1 to 7, respectively.
Carbon anodes 1-7 were applied to the electrolytic aluminum experiments and blank controls were made for carbon anodes that were not coated with paint. The carbon anodes 1 to 7 and the blank group are subjected to an electrolytic aluminum experiment, the purity of the prepared aluminum is almost not different, and the electrolytic aluminum efficiency is equivalent.
the application result shows that: after a period (30 days) of application of the blank group of carbon anodes, the surface of the anodes is seriously oxidized and burnt, edges and corners are almost not, and some phenomena even fall off and pole shedding occur after the carbon anodes are removed, while after a period (30 days) of application of the carbon anodes, the carbon anodes 1-7 are immersed into the surface of the anodes in an electrolyte bath, the edges and corners of the residual carbon anodes are clear and the height of the residual carbon anodes is obviously increased, and after airing and weighing, the carbon anodes 1-8 are respectively 18.2%, 20.3%, 25.1%, 22.5%, 20.9% and 21.6% higher than the blank group in weight.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (8)
1. A method for preparing carbon anode oxidation resistant coating for electrolytic aluminum by comprehensively utilizing aluminum ash is characterized by comprising the following steps: the raw materials comprise the following components in parts by weight: 20-70 parts of aluminum ash, 5-30 parts of strong base, 1-10 parts of aluminum powder, 1-20 parts of boron compound, 0.5-3 parts of organic adhesion promoter and 5-50 parts of water.
2. The method for preparing the carbon anode antioxidant coating for electrolytic aluminum by comprehensively utilizing aluminum ash according to claim 1, characterized by comprising the following steps of: the aluminum ash is generated in at least one process of aluminum casting, aluminum regeneration and aluminum electrolysis.
3. the method for preparing the carbon anode antioxidant coating for electrolytic aluminum by comprehensively utilizing aluminum ash according to claim 1, characterized by comprising the following steps of: the organic adhesion promoter is at least one of carboxymethyl cellulose, polyvinyl alcohol and dextrin.
4. The method for preparing the carbon anode antioxidant coating for electrolytic aluminum by comprehensively utilizing aluminum ash according to claim 1, characterized by comprising the following steps of: the strong base is at least one of sodium hydroxide and potassium hydroxide.
5. the method for preparing the carbon anode antioxidant coating for electrolytic aluminum by comprehensively utilizing aluminum ash according to claim 1, characterized by comprising the following steps of: the boron compound is at least one of sodium borate and boron carbide.
6. The method for preparing the carbon anode antioxidant coating for electrolytic aluminum by comprehensively utilizing aluminum ash according to claim 1, characterized by comprising the following steps of:
1) accurately weighing the raw materials according to the proportion;
2) adding aluminum ash into water, stirring, and keeping the temperature at 50-120 ℃ until no ammonia gas is generated; during which ammonia gas is collected;
3) Cooling the liquid material generated in the step 2) to room temperature, filtering, transferring the filtrate into evaporation equipment to evaporate and recover soluble chloride in the filtrate, and collecting distilled water generated in the evaporation process;
4) adding strong base into distilled water to obtain an alkali solution;
5) adding the filter residue obtained by filtering in the step 3) into an alkali solution, adding aluminum powder, uniformly stirring, and stirring for 5-150 minutes at the temperature of room temperature-150 ℃, wherein the aluminum ash is partially alkali-dissolved in the process, and the alkali-dissolved part directly becomes a coating adhesive; the part of the aluminum ash which is not dissolved by alkali becomes a filler; namely, the product obtained in the process is a mixture of the adhesive and the filler;
6) Adding boron compound and organic adhesion promoter into the mixture of the adhesive and the filler, and uniformly mixing to obtain the carbon anode coating for electrolytic aluminum.
7. The method of claim 6, wherein: the heat preservation time in the step 1) is 1-10 hours.
8. the method of claim 6, wherein: the ammonia gas collecting method comprises the following steps: and introducing ammonia gas into water for collection.
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| CN113652106A (en) * | 2021-09-30 | 2021-11-16 | 王�之 | Wear-resistant paint taking aluminum ash as raw material and preparation method thereof |
| CN115536438A (en) * | 2021-06-30 | 2022-12-30 | 河南晶城新科技材料有限公司 | High-temperature oxidation resistant composite material, preparation method thereof and anode for aluminum electrolysis |
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| CN108315765A (en) * | 2018-04-22 | 2018-07-24 | 新疆大学 | It is a kind of to prepare aluminium electrolysis anode antioxidizing paint using aluminium lime-ash |
| CN108441004A (en) * | 2018-04-20 | 2018-08-24 | 新疆大学 | A kind of apparatus and method preparing aluminium electrolysis anode antioxidizing paint using aluminium lime-ash |
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