CN113231436A - High-temperature recycling treatment method for aluminum electrolysis waste cell lining - Google Patents
High-temperature recycling treatment method for aluminum electrolysis waste cell lining Download PDFInfo
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- 238000004064 recycling Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 85
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 67
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- 239000000292 calcium oxide Substances 0.000 claims description 11
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 9
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- 238000002156 mixing Methods 0.000 claims description 7
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 6
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
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- 238000012546 transfer Methods 0.000 claims description 4
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- 239000011229 interlayer Substances 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
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- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
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- 150000002825 nitriles Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a high-temperature recycling treatment method for aluminum electrolysis waste cell liners, belonging to the technical field of comprehensive utilization of solid waste resources in the aluminum industry. The method adopts a one-step induction heating mode to stack three parts of solid waste raw materials, namely waste cathode carbon blocks, waste silicon carbide side blocks and waste refractory materials, which are contained in a waste tank lining, according to a certain mode, simultaneously adding a proper amount of additives, decomposing cyanide at high temperature in the treatment process, absorbing fluoride by an upper layer covering material after volatilization, cooling the treated material, and screening to obtain a high-graphitization carbon block, silicon carbide particles and aluminum-silicon-calcium mixed material which can be respectively used as a carburant, a deoxidizer and refining slag in the steel refining process. The method has the advantages of clean process, simple treatment device, easy utilization of treated materials and good application prospect.
Description
Technical Field
The invention relates to the technical field of comprehensive utilization of solid waste resources in aluminum industry, in particular to a method for high-temperature recycling treatment of aluminum electrolysis waste cell liners.
Background
The service life of large-scale aluminum electrolytic cells in China is generally 2000 to 3000 days, and when the electrolytic cells are overhauled, the cell linings can be replaced, and a large amount of waste lining solid waste can be produced, wherein the waste lining solid waste comprises waste cathode carbon blocks, waste silicon carbide side blocks and waste refractory materials. The solid waste contains high-level fluoride and cyanide, and is listed in national records of dangerous waste, and the solid waste can cause serious harm to the environment and the atmosphere if the solid waste is naturally stacked and contacted with humid air or rainwater. About 24-30kg of waste tank liners are generated in every 1 ton of aluminum produced by an electrolytic aluminum plant, and about more than 100 million tons of waste tank liners are generated every year according to the current aluminum yield in China, so that a green recycling treatment method is urgently needed to be developed for the huge amount of dangerous solid wastes.
At present, the disposal methods for the aluminum electrolysis waste cell lining at home and abroad mainly comprise a wet method and a fire method.
The treatment research and industrial application of the aluminum electrolytic cell waste cell lining are started earlier abroad. The overhaul slag is treated by adopting a pyrogenic process in a Mei-Al Gum Springs treatment plant, the overhaul slag, quartz and limestone are mixed and then added into a rotary kiln, cyanide is decomposed at high temperature, and soluble fluoride reacts with the limestone to generate calcium fluoride, so that the harmless treatment of the overhaul slag is realized, and the overhaul slag can be buried after being cooled. In 2005, aluminum companies also adopted similar methods to establish 3000 t/year industrial test lines, overhaul residues, limestone, fly ash and the like are respectively crushed and mixed, added into a rotary kiln for calcination, and subjected to fluorine fixation and cyanogen removal to obtain harmless waste residues. However, the waste tank lining can only be harmlessly treated by adopting the pyrometallurgical technology, 1 ton of waste tank lining can produce 1.4 tons of unusable solid waste, and the waste is still dangerous waste according to the existing dangerous waste treatment regulations. Therefore, the technique has not been further applied domestically. Generally, the energy consumption for treating the aluminum electrolysis waste cell lining by adopting the pyrogenic process is high, the investment cost is high, the resource utilization of the waste cell lining cannot be realized, and the pyrogenic process has high requirements on equipment and high development difficulty due to the strong corrosivity of fluoride volatilized at high temperature, so that no technology capable of realizing industrial operation exists at present.
In 2008, the american lyx corporation developed a wet treatment process for "low-caustic lime leaching" of waste tank liners, which employs water and dilute alkali solution to leach cyanide and fluoride in the waste tank liners, removes cyanide in a pressurized reactor, reacts the evaporated concentrate with lime, solidifies and defluorinates, and recycles alkali solution. But the solid waste residue after disposal can not be used. A similar wet treatment line for the waste tank liners is also built in China, soluble fluorine in the waste tank liners is leached by a wet method, meanwhile, calcium hypochlorite and limestone are added to remove cyanide and fix fluorine, and finally, the produced solid waste slag which cannot be utilized is also produced. The wet treatment process has poor economy, and the solid waste slag produced after the waste slot liners are treated cannot be utilized and cannot meet the requirement of environmental protection, so that two or three production lines which are put into production in China currently stop producing.
In contrast, the treatment technology of the waste cell lining for the pyrometallurgical aluminum electrolysis has a greater development prospect, but still faces two main problems, namely, the collection of fluoride gas with strong corrosivity volatilized in the treatment process; and secondly, the utilization of the treated waste slot lining. The waste cathode carbon blocks in the waste tank liners are also used in cement manufacturing and steel industry, wherein the carbon is used for supplementing fuel, and fluoride salt inevitably has certain corrosion effect on equipment.
Disclosure of Invention
The invention aims to provide a method for high-temperature recycling of aluminum electrolysis waste cell liners, which realizes harmless treatment and recycling of dangerous solid wastes of the waste cell liners.
The method comprises the steps of firstly simultaneously treating three solid dangerous wastes of waste cathode carbon blocks, waste silicon carbide side blocks and waste refractory materials in a waste tank lining in a one-step induction heating mode, then realizing rapid heating, heat transfer and efficient absorption of fluoride through particle size control, cooling the treated materials, and then screening to obtain high-graphitization carbon blocks, silicon carbide particles and aluminum, silicon and calcium mixed materials which can be finally respectively used as a carburant, a deoxidizer and refining slag in the refining process of steel refining.
The method specifically comprises the following steps:
(1) classifying and grading: classifying three parts of solid waste of the waste tank lining, and crushing and grading;
(2) distributing in a furnace: preparing a crucible, pre-laying a layer of lime boards at the bottom and on the side wall, and stacking the classified three parts in the crucible;
(3) induction heating: placing the crucible in a medium-frequency magnetic induction coil, quickly raising the temperature of the waste cathode carbon block after electrifying, heating the waste silicon carbide particles in the interlayer by using the waste cathode carbon block, maintaining the heating, volatilizing fluoride salt in the waste cathode carbon block, namely the waste silicon carbide side block, and absorbing the volatilized fluoride salt by alumina and calcium oxide in the waste refractory material after passing through the upper-layer low-temperature covering material;
(4) and (3) grading and recycling: after the high-temperature process is finished, screening the materials according to different particle sizes to respectively obtain high-graphitization carbon blocks, pure silicon carbide particles and covering materials containing calcium fluoride, calcium oxide and calcium aluminate;
(5) and (3) recycling: the obtained highly graphitized carbon block, silicon carbide particles and covering material are further treated and then respectively used as a carburant, a deoxidizer and refining slag raw materials in the steelmaking process.
Wherein, the crushing particle size requirement of the three parts of solid waste in the step (1) is as follows: the waste cathode carbon block is crushed to 30-100mm, the waste silicon carbide side block is crushed to 1-10mm, and the waste refractory material is crushed to less than 150 mu m.
The mode of stacking the three parts in the crucible in the step (2) is specifically as follows: the waste cathode carbon blocks and the waste silicon carbide are stacked at intervals in a layered mode, the waste cathode carbon blocks are stacked in 2-6 layers according to the size of a crucible, and the waste silicon carbide particles are stacked in 1-5 layers; ensuring that the bottommost layer and the topmost layer are waste cathode carbon block materials, and stacking the waste cathode carbon blocks and the waste silicon carbide particles in each layer according to the mass ratio of 2: 1; mixing the waste refractory material and lime according to the mass ratio of 0.5-2, and stacking the mixture as a covering material above the topmost waste cathode carbon block, wherein the particle size of the lime is less than 1mm, and the mass ratio of the mixture of the waste refractory material and the lime to the mass of all the waste cathode carbon blocks and the waste silicon carbide particles is 0.1-1.
In the step (2), the crucible is one of corundum, magnesium chrome or magnesia crucible, and graphite or metal crucible can not be used.
The heating temperature range in the step (3) is 1500-.
In the step (4), after sieving, oversize materials of more than 30mm are high graphitized carbon blocks, sieving materials of 1-10mm are silicon carbide particles, undersize materials of less than 150 mu m are covering materials, and the rest intermediate materials are directly used as deoxidizing agents for steelmaking; meanwhile, in order to promote the precipitation of fluoride, inert gas is introduced into the bottom of the crucible.
The further treatment of the high graphitized carbon block in the step (5) specifically comprises the following steps: further crushing the screened high-graphitization carbon block to be less than 75 mu m, adding 1-5% of binder according to the mass ratio, and pressing the high-graphitization carbon block into a granular or blocky material with the thickness of 1-50mm, or mixing the high-graphitization carbon block with calcined coke and electrically calcined coal according to the mass ratio of 5-50% and pressing the high-graphitization carbon block; or directly crushing the highly graphitized carbon block to the granularity of 1-50 mm; drying the formed granular or block materials at the temperature of 100-150 ℃ for 0.5-2 hours, wherein the dried materials can be used as carburant raw materials in the process of converter or electric furnace steelmaking.
The further treatment of the silicon carbide particles in the step (5) is specifically as follows: the SiC content in the silicon carbide particles obtained by screening is more than 90 percent, and the silicon carbide particles can be directly used as a deoxidizing agent for steelmaking; or grinding the mixture to be less than 75 mu m, mixing the mixture with the mixture of the iron ore concentrate and the waste iron sheet according to the mass ratio of 1:20-1:2, carrying out high-temperature treatment at 1500 ℃ for 1-2 hours through 1000-one, cooling, adding 1-5% of a binder according to the mass ratio for granulation, and drying at 150 ℃ for 0.5-2 hours through 100-one to obtain a mixed particle material serving as a deoxidizing agent for steelmaking.
The further treatment of the covering material in the step (5) is specifically as follows: directly granulating the screened covering material to be used as mixed steelmaking refining slag for steelmaking; or granulating after sintering at 1300 ℃ and using as sintering type steelmaking refining slag; or according to the specific components of the covering material, according to the requirements of YB/T4265-.
The technical scheme of the invention has the following beneficial effects:
according to the scheme, three parts of solid waste of the waste cell lining are stacked in a crucible in different particle sizes, an electromagnetic induction heating mode is adopted, the waste cathode carbon block is heated rapidly, the waste silicon carbide side block is further heated, a waste refractory material and lime are mixed according to a certain proportion to serve as a top covering material and be used for absorbing volatile fluoride, and the high-graphitization carbon material, the silicon carbide material and the aluminum-silicon-calcium mixture which are obtained after the high-temperature treatment and the product are screened according to the particle sizes can be used as a carburant, a deoxidizer and refining slag in the steelmaking process respectively, so that the harmless disposal and the resource utilization of the waste cell lining of the aluminum electrolysis cell are realized.
Drawings
FIG. 1 is a schematic diagram of an apparatus for carrying out the method of the present invention;
FIG. 2 is a flow chart of the method of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
The invention provides a high-temperature recycling treatment method for aluminum electrolysis waste cell liners.
As shown in figure 1, which is a schematic diagram of the device of the method, as shown in figure 2, the method firstly adopts a one-step induction heating mode to simultaneously treat three solid dangerous wastes in a waste tank lining, then realizes rapid heating, heat transfer and efficient absorption of fluoride through granularity control, and after the treated materials are cooled, the materials are screened to obtain a high-graphitization carbon block, silicon carbide particles and an aluminum-silicon-calcium mixed material which can be finally respectively used as a carburant, a deoxidizer and refining slag in the refining process of steel refining.
The method specifically comprises the following steps:
(1) classifying and grading: classifying three parts of solid waste of the waste tank lining, and crushing and grading;
(2) distributing in a furnace: preparing a crucible, pre-laying a layer of lime boards at the bottom and on the side wall, and stacking the classified three parts in the crucible;
the fluoride salt volatilized from the waste cathode carbon block and the waste silicon carbide side block is absorbed by the lime plate at the bottom of the side part and the covering material at the upper layer, so that the fluoride is effectively prevented from volatilizing into the treated flue gas and corroding the furnace lining, the lime plate at the bottom of the side part can be used as the covering material after being broken, the covering material can be recycled for multiple times, and the fluoride can be recycled after being enriched to a certain degree.
(3) Induction heating: placing the crucible in a medium-frequency magnetic induction coil, quickly raising the temperature of the waste cathode carbon block after electrifying, heating the waste silicon carbide particles in the interlayer by using the waste cathode carbon block, maintaining the heating, volatilizing fluoride salt in the waste cathode carbon block, namely the waste silicon carbide side block, and absorbing the volatilized fluoride salt by alumina and calcium oxide in the waste refractory material after passing through the upper-layer low-temperature covering material;
(4) and (3) grading and recycling: after the high-temperature process is finished, screening the materials according to different particle sizes to respectively obtain high-graphitization carbon blocks, pure silicon carbide particles and covering materials containing calcium fluoride, calcium oxide and calcium aluminate;
(5) and (3) recycling: the obtained highly graphitized carbon block, silicon carbide particles and covering material are further treated and then respectively used as a carburant, a deoxidizer and refining slag raw materials in the steelmaking process.
The following description is given with reference to specific examples.
Examples
A method for harmlessly disposing and recycling waste cell liners of aluminum electrolysis cells comprises the following steps:
1. preparing 100g of waste cathode carbon blocks with the particle size of 30-35mm, 25g of waste silicon carbide with the particle size of 1mm, and 100g of a covering material formed by mixing a waste refractory material with the particle size of less than 100 mu m and 100g of calcium oxide powder;
2. preparing a corundum crucible with the wall thickness of 5mm, the inner diameter of 80mm and the height of 200mm and a calcium oxide crucible with the wall thickness of 5mm, the inner diameter of 70mm and the height of 190 mm; placing a calcium oxide crucible in a corundum crucible;
3. adding materials into a prepared crucible from bottom to top according to the sequence of 50g of waste carbon blocks, 25g of waste silicon carbide particles, 50g of waste carbon blocks and 200g of covering materials, placing the crucible into an induction heating coil, and placing the bottom waste carbon block materials in the middle of the induction coil;
4. electrifying the coil, heating the materials to about 1700 ℃, maintaining the induction heating state for 30 minutes to fully volatilize fluoride in the bottom layer materials, and naturally cooling to room temperature after heating;
5. screening to obtain: about 86.2g of highly graphitized carbon block (oversize with a diameter of more than 20 mm), 24.1g of silicon carbide particles (screen with a diameter of 0.5-1 mm) and 213.6g of cover mix (undersize with a diameter of less than 100 μm); the rest materials are lost or directly used as a deoxidizing agent for steelmaking;
6. the detection and analysis result shows that the fixed carbon content in the high-graphitization carbon block is more than 95 percent and can be used as a carburant for steelmaking; the SiC content in the silicon carbide particles is more than 90 percent, and the silicon carbide particles can be used as a deoxidizing agent for steelmaking; the covering material mixture contains 38.1 percent of calcium oxide, 31.7 percent of aluminum oxide, 8.1 percent of silicon dioxide and 10.4 percent of calcium fluoride respectively, and can be used as a mixed steel-making refining agent.
The invention provides a method for high-temperature resource utilization of waste aluminum electrolytic cell linings, which comprises the steps of treating the waste cell linings in an electromagnetic induction heating mode, stacking three parts of solid waste raw materials, namely waste cathode carbon blocks, waste silicon carbide side blocks and waste refractory materials, contained in the waste cell linings according to a certain mode, simultaneously adding a proper amount of additives, decomposing cyanides at high temperature in the treatment process, absorbing fluorides by upper covering materials after volatilization, and respectively using the three parts of treated materials as auxiliary raw materials in a steelmaking process. The method has the advantages of clean process, simple treatment device, easy utilization of treated materials and good application prospect.
The invention well solves the problems that the manufacturing difficulty of a processing device is high, the strength is reduced after the lining material is seriously corroded, and volatile matters are not easy to supplement and collect caused by the strong corrosive fluoride volatile gas generated in the process of processing the waste tank lining by a high-temperature pyrogenic process, and the volatile fluoride salt gas is absorbed and converted into the calcium fluoride which is difficult to volatilize by adopting a covering material absorption mode and is fixedly retained in the covering material.
The invention uses the respective characteristics of three solid waste materials, utilizes a particle size control mode, can realize the separation of the three materials by simple screening, and uses the waste cathode carbon block as an induction heating material, the particle size of which is as large as possible, so as to fully absorb electromagnetic waves and rapidly heat the material; the silicon carbide material is about 1mm granular and is fully filled in gaps of the waste cathode carbon blocks, so that the heat transfer efficiency is increased; the upper covering material is fine in particle size and powdery so as to generate enough surface area and quickly absorb volatilized fluoride salt to prevent the fluoride salt from overflowing.
In addition, the invention also solves the economic treatment and utilization problems of the waste slot liners, and adopts a one-step heating mode to heat the waste cathode carbon blocks and the waste silicon carbide particles at the bottom layer and the middle part to high temperature so as to volatilize the fluoride in a gaseous state; the upper covering material can also be used as a heat insulating material, and the temperature is low and does not reach the volatilization temperature of fluoride, so that the components of alumina and calcium oxide in the upper covering material can retain volatilized fluoride salt in the upper covering material. The high graphitized carbon material, the silicon carbide material and the calcium-aluminum-silicon mixed material are obtained after treatment, and can be applied to the steel industry as a carburant, a deoxidizer and a refining slag auxiliary raw material in the steel-making refining process according to the properties of the high graphitized carbon material, the silicon carbide material and the calcium-aluminum-silicon mixed material, so that the high graphitized carbon material, the silicon carbide material and the calcium-aluminum-silicon mixed material are completely recycled.
The technology realizes the harmless disposal and the classified utilization of the solid dangerous waste of the aluminum electrolysis waste cell lining by a primary induction heating treatment mode, and has the advantages of simple whole process flow, no secondary pollutant in the process, good economic benefit and better application prospect.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method for high-temperature resource treatment of aluminum electrolysis waste cell liners is characterized by comprising the following steps: the method comprises the steps of firstly, simultaneously treating three solid dangerous wastes of waste cathode carbon blocks, waste silicon carbide side blocks and waste refractory materials in a waste tank lining in a one-step induction heating mode, then realizing rapid heating, heat transfer and efficient absorption of fluoride through particle size control, cooling the treated materials, and then screening to obtain high-graphitization carbon blocks, silicon carbide particles and aluminum-silicon-calcium mixed materials which can be finally used as carburant, deoxidizer and refining slag in the steel-making refining process.
2. The method for high-temperature resource treatment of the aluminum electrolysis waste cell lining as claimed in claim 1, wherein the method comprises the following steps: the method comprises the following steps:
(1) classifying and grading: classifying three parts of solid waste of the waste tank lining, and crushing and grading;
(2) distributing in a furnace: preparing a crucible, pre-laying a layer of lime boards at the bottom and on the side wall, and stacking the classified three parts in the crucible;
(3) induction heating: placing the crucible in a medium-frequency magnetic induction coil, quickly raising the temperature of the waste cathode carbon block after electrifying, heating the waste silicon carbide particles in the interlayer by using the waste cathode carbon block, maintaining the heating, volatilizing fluoride salt in the waste cathode carbon block, namely the waste silicon carbide side block, and absorbing the volatilized fluoride salt by alumina and calcium oxide in the waste refractory material after passing through the upper-layer low-temperature covering material;
(4) and (3) grading and recycling: after the high-temperature process is finished, screening the materials according to different particle sizes to respectively obtain high-graphitization carbon blocks, pure silicon carbide particles and covering materials containing calcium fluoride, calcium oxide and calcium aluminate;
(5) and (3) recycling: the obtained highly graphitized carbon block, silicon carbide particles and covering material are further treated and then respectively used as a carburant, a deoxidizer and refining slag raw materials in the steelmaking process.
3. The method for high-temperature resource treatment of the aluminum electrolysis waste cell lining as claimed in claim 2, wherein the method comprises the following steps: the crushing particle size requirement of the three parts of solid waste in the step (1) is as follows: the waste cathode carbon block is crushed to 30-100mm, the waste silicon carbide side block is crushed to 1-10mm, and the waste refractory material is crushed to less than 150 mu m.
4. The method for high-temperature resource treatment of the aluminum electrolysis waste cell lining as claimed in claim 2, wherein the method comprises the following steps: the mode that three parts are stacked in the crucible in the step (2) is specifically as follows: the waste cathode carbon blocks and the waste silicon carbide are stacked at intervals in a layered mode, the waste cathode carbon blocks are stacked in 2-6 layers according to the size of a crucible, and the waste silicon carbide particles are stacked in 1-5 layers; ensuring that the bottommost layer and the topmost layer are waste cathode carbon block materials, and stacking the waste cathode carbon blocks and the waste silicon carbide particles in each layer according to the mass ratio of 2: 1; mixing a waste refractory material and lime according to a mass ratio of 0.5-2, and stacking the mixture as a covering material above the topmost waste cathode carbon block, wherein the particle size of the lime is less than 1 mm; the mass ratio of the mixture composed of the waste refractory material and the lime to the mass of all the waste cathode carbon blocks and the waste silicon carbide particle materials is 0.1-1.
5. The method for high-temperature resource treatment of the aluminum electrolysis waste cell lining as claimed in claim 2, wherein the method comprises the following steps: the crucible in the step (2) is one of corundum, magnesium chrome or magnesia crucible.
6. The method for high-temperature resource treatment of the aluminum electrolysis waste cell lining as claimed in claim 2, wherein the method comprises the following steps: the heating temperature in the step (3) is 1500-.
7. The method for high-temperature resource treatment of the aluminum electrolysis waste cell lining as claimed in claim 2, wherein the method comprises the following steps: in the step (4), oversize materials of more than 30mm after screening are high-graphitization carbon blocks, screening materials of 1-10mm are silicon carbide particles, and undersize materials of less than 150 mu m are covering materials; the rest intermediate materials are directly used as deoxidizing agents for steelmaking; meanwhile, in the step (4), in order to promote the precipitation of the fluoride, inert gas is introduced into the bottom of the crucible.
8. The method for high-temperature resource treatment of the aluminum electrolysis waste cell lining as claimed in claim 2, wherein the method comprises the following steps: the further treatment of the high graphitized carbon block in the step (5) specifically comprises the following steps: further crushing the screened high-graphitization carbon block to be less than 75 mu m, adding 1-5% of binder according to the mass ratio, and pressing the high-graphitization carbon block into a granular or blocky material with the thickness of 1-50mm, or mixing the high-graphitization carbon block with calcined coke and electrically calcined coal according to the mass ratio of 5-50% and pressing the high-graphitization carbon block; or directly crushing the highly graphitized carbon block to the granularity of 1-50 mm; drying the formed granular or block materials at the temperature of 100-150 ℃ for 0.5-2 hours, and taking the dried materials as carburant raw materials in the process of converter or electric furnace steelmaking.
9. The method for high-temperature resource treatment of the aluminum electrolysis waste cell lining as claimed in claim 2, wherein the method comprises the following steps: the further treatment of the silicon carbide particles in the step (5) is specifically as follows: the SiC content in the silicon carbide particles obtained by screening is more than 90 percent, and the silicon carbide particles are directly used as a deoxidizing agent for steelmaking; or grinding the mixture to be less than 75 mu m, mixing the mixture with the mixture of the iron ore concentrate and the waste iron sheet according to the mass ratio of 1:20-1:2, carrying out high-temperature treatment at 1500 ℃ for 1-2 hours through 1000-one, cooling, adding 1-5% of a binder according to the mass ratio for granulation, and drying at 150 ℃ for 0.5-2 hours through 100-one to obtain a mixed particle material serving as a deoxidizing agent for steelmaking.
10. The method for high-temperature resource treatment of the aluminum electrolysis waste cell lining as claimed in claim 2, wherein the method comprises the following steps: the further treatment of the covering material in the step (5) is specifically as follows: directly granulating the screened covering material to be used as mixed steelmaking refining slag for steelmaking; or granulating after sintering at 1300 ℃ and using as sintering type steelmaking refining slag; or according to the specific components of the covering material, according to the requirements of YB/T4265-.
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---|---|---|---|---|
CN114433598A (en) * | 2022-02-14 | 2022-05-06 | 季秀女 | Treatment method of electrolytic aluminum |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES8500772A1 (en) * | 1983-03-01 | 1984-11-01 | Alcan Int Ltd | Treatment of scrap lining material from aluminium reduction cells. |
CN102978659A (en) * | 2012-12-04 | 2013-03-20 | 贵州铝城铝业原材料研究发展有限公司 | Deep comprehensive resource utilization method for electrolytic cell overhaul slag |
CN104975308A (en) * | 2015-07-11 | 2015-10-14 | 云南云铝润鑫铝业有限公司 | Aluminum electrolytic waste slot lining closed-loop recycling method |
CN107720723A (en) * | 2017-11-09 | 2018-02-23 | 北京科技大学 | A kind of method of overall treatment aluminium electrolytic tank |
CN108994051A (en) * | 2018-07-23 | 2018-12-14 | 江苏中商碳素研究院有限公司 | The treatment process of waste material in aluminium cell |
CN110117718A (en) * | 2019-05-15 | 2019-08-13 | 东北大学 | The method for producing ferro-silicon-aluminium as raw material electric arc furnace smelting using waste refractory materials |
-
2021
- 2021-04-13 CN CN202110398659.7A patent/CN113231436B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES8500772A1 (en) * | 1983-03-01 | 1984-11-01 | Alcan Int Ltd | Treatment of scrap lining material from aluminium reduction cells. |
CN102978659A (en) * | 2012-12-04 | 2013-03-20 | 贵州铝城铝业原材料研究发展有限公司 | Deep comprehensive resource utilization method for electrolytic cell overhaul slag |
CN104975308A (en) * | 2015-07-11 | 2015-10-14 | 云南云铝润鑫铝业有限公司 | Aluminum electrolytic waste slot lining closed-loop recycling method |
CN107720723A (en) * | 2017-11-09 | 2018-02-23 | 北京科技大学 | A kind of method of overall treatment aluminium electrolytic tank |
CN108994051A (en) * | 2018-07-23 | 2018-12-14 | 江苏中商碳素研究院有限公司 | The treatment process of waste material in aluminium cell |
CN110117718A (en) * | 2019-05-15 | 2019-08-13 | 东北大学 | The method for producing ferro-silicon-aluminium as raw material electric arc furnace smelting using waste refractory materials |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114433598A (en) * | 2022-02-14 | 2022-05-06 | 季秀女 | Treatment method of electrolytic aluminum |
CN114433598B (en) * | 2022-02-14 | 2024-05-03 | 巩义新格新材料有限公司 | Electrolytic aluminum treatment method |
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