CN114589293A - Method for preparing continuous casting covering slag by using electrolytic aluminum waste residue, waste water and blast furnace slag - Google Patents
Method for preparing continuous casting covering slag by using electrolytic aluminum waste residue, waste water and blast furnace slag Download PDFInfo
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- CN114589293A CN114589293A CN202210347379.8A CN202210347379A CN114589293A CN 114589293 A CN114589293 A CN 114589293A CN 202210347379 A CN202210347379 A CN 202210347379A CN 114589293 A CN114589293 A CN 114589293A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/10—Supplying or treating molten metal
- B22D11/11—Treating the molten metal
- B22D11/111—Treating the molten metal by using protecting powders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/16—Controlling or regulating processes or operations
- B22D11/22—Controlling or regulating processes or operations for cooling cast stock or mould
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
Abstract
The invention discloses a method for preparing continuous casting covering slag by using electrolytic aluminum waste residue, waste water and blast furnace slag, which comprises the following steps: firstly, the covering slag takes 22-45% of calcium oxide, 17-56% of silicon oxide and 0-13% of aluminum oxide as basic slag, the melting point of the covering slag is controlled to be about 900-1100 ℃ by adding a material containing 2-16% of fluorine and 2-20% of sodium as a solvent, and the melting rate of the covering slag is controlled by utilizing the principle that carbon and slag are not infiltrated after 2-20% of carbon material is added; according to the invention, the blast furnace slag solid waste and the SPL dangerous waste are converted into the production raw materials of the covering slag, and when the covering slag is used, the sodium fluoride and the calcium silicate are converted into the gunite by using the heat of steel continuous casting, so that the solid waste treatment is realized without additional energy and reagents.
Description
Technical Field
The invention relates to the technical field of continuous casting covering slag, in particular to a method for preparing continuous casting covering slag by utilizing electrolytic aluminum waste residue, waste water and blast furnace slag.
Background
Aluminum is one of the most important metallic materials, and its yield is second only to steel. The total yield of electrolytic aluminum worldwide in 2020 is 6700 ten thousand tons. Currently, the Hall-Elut method, namely an electrolytic aluminum oxide molten salt method, which has a history of more than a hundred years, is still adopted for producing aluminum. In the production process of electrolytic aluminum, the lining structure of the electrolytic cell is deformed and broken due to the permeation and corrosion of the molten high-temperature electrolyte, and aluminum liquid and the electrolyte in the electrolytic cell leak into the bottom of the electrolytic cell from cracks, so that the electrolytic cell cannot be normally used. Therefore, the aluminum electrolysis cell needs to be overhauled on average every 5 to 8 years, and the cathode lining material removed in the process is called electrolytic aluminum overhaul slag SPL (SpentPotlining). 20-30 kg of overhaul slag is generated every 1 ton of aluminum is produced on average. About 140 million tons of SPL will be produced in 2020. The main components of the overhaul slag mainly comprise 7.5 to 22 percent of fluoride, 8.6 to 22 percent of sodium, 9.2 to 26 percent of alumina and 0.04 to 0.6 percent of cyanide. In 2016, the national records of dangerous wastes define the electrolytic aluminum overhaul residues as dangerous wastes, and the danger codes are HW 48-321-023-48. In addition, the environmental protection tax of the hazardous waste is 1000 yuan/ton as specified in the environmental protection tax Law of the people's republic of China which is executed from 2018, 1 month and 1 day. In addition, in the electrolytic aluminum production, in order to eliminate the volatilization of sodium fluoride, aluminum fluoride and other substances in cryolite at high temperature, a wet method treatment is adopted to remove volatile matters, and a large amount of fluorine-containing sodium-containing wastewater is generated in the treatment process.
At present, the SPL is treated by three main ways, the first way is landfill, and the first way is that substances such as fluoride, cyanide and the like in the buried SPL can enter surface water and underground water along with rainfall release, harmful gases such as hydrogen fluoride and the like are released, the atmosphere is polluted, the growth of animals and plants is damaged, and the environment is polluted. Landfill is currently almost eliminated as an early form of SPL treatment. The second is wet treatment, fluoride dissolved in water in the SPL is separated from cyanide from fixed carbon by water, then the fixed carbon which is not dissolved in water is recovered to be used as fuel, and the silicon-aluminum oxide which is not dissolved in water is recovered to be used as a cement-based raw material. A large amount of generated fluorine-containing cyanide-containing wastewater is adsorbed by materials such as activated alumina, activated carbon, nano materials and the like, and then fluorine and cyanide in water are removed in a filter membrane filtration mode, however, the water treatment method is complex in process, the cost of a desorption agent is often high, and heavy metals possibly brought in the processes of defluorination and decyanation in water cause secondary pollution of water. And the third is pyrogenic process, wherein the SPL, coal, sludge and other substances are uniformly mixed, cyanide is combusted and decomposed at high temperature, unstable sodium fluoride in the SPL, the coal, calcium silicate and calcium oxide in the sludge are subjected to solid-phase reaction, and the sodium fluoride which is soluble in water and has a lower melting point is converted into calcium fluoride or kyanite which is insoluble in water and has a higher melting point. Therefore, dangerous solid waste is converted into common solid waste, the effect of fluorine fixation is achieved, and meanwhile, heat can be provided by burning of carbon materials such as graphite and the like. The pyrogenic process has high conversion efficiency and simple process, but because the pyrogenic process needs to additionally consume a large amount of energy and increase the additional cost, the combustion temperature of the graphite is also higher, and the higher combustion temperature can cause the fluoride to volatilize at high temperature.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a method for preparing continuous casting covering slag by using electrolytic aluminum waste residue, waste water and blast furnace slag, which has the effects of taking fluorine-containing waste water of an electrolytic aluminum plant as a water source of covering slag slurry, precipitating fluoride dissolved in water into the covering slag through high-temperature granulation, and converting dangerous solid waste into products by using the heat of continuous casting steel.
In order to achieve the purpose, the invention provides the following technical scheme: the method for preparing the continuous casting covering slag by utilizing the electrolytic aluminum waste residue, the waste water and the blast furnace slag comprises the following steps:
firstly, the covering slag takes 22-45% of calcium oxide, 17-56% of silicon oxide and 0-13% of aluminum oxide as basic slag, the melting point of the covering slag is controlled to be about 900-1100 ℃ by adding a material containing 2-16% of fluorine and 2-20% of sodium as a solvent, and the melting rate of the covering slag is controlled by utilizing the principle that carbon and slag are not infiltrated after 2-20% of carbon material is added;
step two, although the use temperature of the covering slag reaches 1550 ℃ at most, sodium fluoride generated by a slag layer cannot escape from the surface of the covering slag due to the covering of a covering slag sintering layer and a powder slag layer at high temperature, and the covering slag realizes the control of casting blank cooling by forming gunite to change heat transfer in the casting blank cooling process of a crystallizer;
step three, the casting powder undergoes a thermal process of firstly heating and then cooling, so that a three-layer structure of a slag layer, a sintering layer and a powder slag layer is formed on the surface of a casting blank, and as the powder slag of the casting powder has large dust, and in order to meet the requirement of automatic slag addition, the casting powder firstly uniformly mixes powder slag, water and a binder to prepare slurry, and then the formed slurry is prepared into a hollow granular slag product through high-temperature spray granulation;
step four, water can be rapidly evaporated in the spray granulation process, sodium fluoride and cyanide dissolved in the water can be separated out to the surface of the hollow particle protective slag, the blast furnace slag solid waste and the SPL hazardous waste are converted into production raw materials of the protective slag, the sodium fluoride and the calcium silicate are converted into the gunite by utilizing the heat of steel continuous casting in the using process of the protective slag, and the solid waste treatment is realized without extra energy and reagents.
Preferably, the common process of steel smelting is to make iron first and then steel, and a large amount of high slag is produced through blast furnace iron making.
Preferably, 97% of steel produced by converter steelmaking is produced by continuous casting.
Preferably, the continuous casting covering slag as a key functional material of the continuous casting billet has five functions of lubricating the casting billet, controlling heat transfer, preventing secondary oxidation of molten steel, absorbing molten steel inclusions and insulating heat.
Preferably, from the viewpoint of elemental composition, SPL can provide fluorine, sodium, carbon, aluminum elements required for mold flux.
Preferably, the blast furnace slag can provide calcium, silicon and aluminum elements required by the covering slag.
Preferably, the SPL is adjusted by testing the contents of the SPL and the blast furnace slag through XRF, the proportion of the waste water and the blast furnace slag is used for preparing the continuous casting mold flux, and the component contents of the mold flux are verified through XRF.
Preferably, the XRF is an X-ray fluorescence analyzer.
Preferably, the SPL and the blast furnace slag can be matched with the similarity of the components of the covering slag, and the fluorine-containing wastewater of an electrolytic aluminum plant can be used as a water source of the covering slag slurry by utilizing the characteristics of the covering slag production process.
Preferably, fluoride dissolved in water is precipitated to mold flux by high temperature granulation, and dangerous solid wastes are converted into products by using heat of continuous casting steel.
Compared with the prior art, the invention provides the method for preparing the continuous casting covering slag by utilizing the electrolytic aluminum waste residue, the waste water and the blast furnace slag, and the method has the following beneficial effects:
1. according to the invention, the blast furnace slag solid waste and the SPL dangerous waste are converted into the production raw materials of the covering slag, and when the covering slag is used, the sodium fluoride and the calcium silicate are converted into the gunite by using the heat of steel continuous casting, so that the solid waste treatment is realized without additional energy and reagents.
2. By treating the SPL hazardous waste and the fluorine-containing wastewater, the production cost of the protective slag factory can be greatly reduced, the environment is protected, the carbon emission is reduced, and the raw materials such as fluorite, sodium carbonate, graphite, tap water and the like which are originally required to be purchased by the protective slag factory are saved.
Drawings
FIG. 1 is a schematic view of a three-layer structure and a temperature gradient model of mold flux according to the present invention;
FIG. 2 is a schematic diagram of a sodium fluoride cycle model according to the present invention;
FIG. 3 is a schematic view showing a process for preparing a mold flux slurry according to the present invention;
FIG. 4 is a schematic view of a process for preparing a hollow granular mold flux according to the present invention.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
Referring to fig. 1-4, the present invention provides a technical solution: the method for preparing the continuous casting covering slag by utilizing the electrolytic aluminum waste residue, the waste water and the blast furnace slag comprises the following steps:
firstly, the covering slag takes 22-45% of calcium oxide, 17-56% of silicon oxide and 0-13% of aluminum oxide as basic slag, the melting point of the covering slag is controlled to be about 900-1100 ℃ by adding a material containing 2-16% of fluorine and 2-20% of sodium as a solvent, and the melting rate of the covering slag is controlled by utilizing the principle that carbon and slag are not infiltrated after 2-20% of carbon material is added;
step two, although the use temperature of the casting powder is up to 1550 ℃, sodium fluoride generated by a slag layer cannot escape from the surface of the casting powder due to the covering of a casting powder sintering layer and a powder slag layer at high temperature, the sodium fluoride circulation process is shown in figure 2, and in the casting blank cooling process of a crystallizer, the casting powder realizes the control of casting blank cooling by forming gunite to change heat transfer;
step three, the casting powder undergoes a thermal process of firstly heating and then cooling, so that a three-layer structure of a slag layer, a sintering layer and a powder slag layer is formed on the surface of a casting blank, the using environment of the casting powder is shown in figure 1, the casting powder is prepared into slurry after uniformly mixing the powder slag, water and a binder for meeting the requirement of automatic slag adding, the production process is shown in figure 3, and then the formed slurry is prepared into a hollow granular slag product through high-temperature spray granulation;
step four, water is rapidly evaporated in the spray granulation process, sodium fluoride and cyanide dissolved in the water are separated out to the surface of the hollow particle casting powder, the production process is shown in figure 4, the blast furnace slag solid waste and the SPL hazardous waste are converted into production raw materials of the casting powder, and when the casting powder is used, the sodium fluoride and the calcium silicate are converted into the gunite by using the heat of steel continuous casting, so that the solid waste treatment is realized without extra energy and reagents.
In the invention, preferably, the common process of steel smelting is to make iron and then steel, and a large amount of high slag can be generated by blast furnace iron making.
In the present invention, it is preferable that 97% of steel produced by converter steelmaking is produced by continuous casting.
In the invention, preferably, the continuous casting covering slag is used as a key functional material of the continuous casting billet and has five functions of lubricating the casting billet, controlling heat transfer, preventing secondary oxidation of molten steel, absorbing molten steel inclusions and insulating heat.
In the present invention, preferably, from the viewpoint of elemental composition, SPL can provide fluorine, sodium, carbon, and aluminum elements required for mold flux.
In the present invention, preferably, the blast furnace slag can provide calcium, silicon and aluminum elements required for the mold flux.
In the invention, preferably, the SPL is adjusted by testing the contents of the SPL and the blast furnace slag through XRF, the continuous casting mold flux is prepared by the proportion of the waste water and the blast furnace slag, and the component contents of the mold flux are verified through XRF.
In the present invention, preferably, the XRF is an X-ray fluorescence analyzer.
In the invention, preferably, the SPL and the blast furnace slag can be matched with the similarity of the components of the covering slag, and the fluorine-containing wastewater of an electrolytic aluminum plant can be used as a water source of the covering slag slurry by utilizing the characteristics of the production process of the covering slag.
In the present invention, it is preferable that fluoride dissolved in water is precipitated to mold flux by granulation at high temperature, and dangerous solid wastes are converted into products by using heat of continuous casting steel.
Example one
The method for preparing continuous casting covering slag by utilizing electrolytic aluminum waste residue, waste water and blast furnace slag comprises the steps of taking 22-45% of calcium oxide, 17-56% of silicon oxide and 0-13% of aluminum oxide as basic slag, adding a material containing 2-16% of fluorine and 2-20% of sodium as a solvent to control the melting point of the covering slag to be about 900-1100 ℃, and controlling the melting rate of the covering slag by utilizing the principle that carbon and slag are not infiltrated after 2-20% of carbon material is added; although the use temperature of the covering slag reaches 1550 ℃ at the maximum, sodium fluoride generated in a slag layer cannot escape from the surface of the covering slag due to the covering of a sintering layer and a powder slag layer of the covering slag at high temperature, the sodium fluoride circulation process is shown in figure 2, and the covering slag changes heat transfer by forming barytes in the casting blank cooling process of a crystallizer to realize the control of the casting blank cooling; the casting powder undergoes a thermal history of first heating and then cooling, so that a three-layer structure of a slag layer, a sintering layer and a powder slag layer is formed on the surface of a casting blank, the using environment of the casting powder is shown in figure 1, the powder slag, water and a binder are uniformly mixed to prepare slurry for the casting powder in order to meet the requirement of automatic slag adding, the production process is shown in figure 3, and then the formed slurry is prepared into a hollow granular slag product through high-temperature spray granulation; in the spray granulation process, water is quickly evaporated, sodium fluoride and cyanide dissolved in the water are separated out to the surface of the hollow particle casting powder, the production process is shown in figure 4, the blast furnace slag solid waste and the SPL hazardous waste are converted into production raw materials of the casting powder, and when the casting powder is used, the sodium fluoride and the calcium silicate are converted into gunite by using the heat of steel continuous casting, so that the solid waste treatment is realized without extra energy and reagents.
Example two
The common process of steel smelting is that the steel is smelted after the iron is smelted, a large amount of high slag is produced through blast furnace iron smelting, 97% of steel is smelted by a converter in a continuous casting mode, continuous casting protective slag is used as a key functional material of a continuous casting billet and has five major functions of lubricating the casting billet, controlling heat transfer, preventing secondary oxidation of molten steel, absorbing molten steel inclusions and insulating heat, from the aspect of element components, SPL can provide fluorine, sodium, carbon and aluminum elements required by the protective slag, blast furnace slag can provide calcium, silicon and aluminum elements required by the protective slag, SPL is adjusted by testing the content of the SPL and the blast furnace slag through XRF, the continuous casting protective slag is prepared according to the proportion of waste water and the blast furnace slag, the component content of the protective slag is verified through XRF, XRF is an X-ray fluorescence analyzer, the similarity of the SPL and the blast furnace slag components can be matched with the protective slag, and by utilizing the characteristics of the protective slag production process, fluorine-containing waste water of an electrolytic aluminum factory can be used as a water source of protective slag slurry, through high-temperature granulation, fluoride dissolved in water is separated out to the covering slag, and dangerous solid waste is converted into a product by utilizing the heat of continuous casting steel.
The working principle and the using process of the invention are as follows: when the protective slag is used, the SPL can provide fluorine, sodium, carbon and aluminum elements required by the protective slag, the blast furnace slag can provide calcium, silicon and aluminum elements required by the protective slag, the SPL is adjusted by testing the contents of the SPL and the blast furnace slag through an XRF (X-ray fluorescence analyzer), the proportion of waste water and the blast furnace slag is used for preparing the continuous casting protective slag, and the XRF is used for verifying the component contents of the protective slag. The raw material of the covering slag is changed along with steel products and continuous casting conditions, the waste material of the SPL is also fluctuant along with the electrolytic aluminum process conditions, the SPL and the blast furnace slag can be matched with the similarity of the components of the covering slag, the fluorine-containing waste water of an electrolytic aluminum factory can be used as the water source of the covering slag slurry by utilizing the characteristics of the covering slag production process, through high-temperature granulation, fluoride dissolved in water is separated out to the covering slag, and the dangerous solid waste is converted into a product by utilizing the heat of continuous casting steel.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A method for preparing continuous casting covering slag by utilizing electrolytic aluminum waste residue, waste water and blast furnace slag is characterized by comprising the following steps:
firstly, the covering slag takes 22-45% of calcium oxide, 17-56% of silicon oxide and 0-13% of aluminum oxide as basic slag, the melting point of the covering slag is controlled to be about 900-1100 ℃ by adding a material containing 2-16% of fluorine and 2-20% of sodium as a solvent, and the melting rate of the covering slag is controlled by utilizing the principle that carbon and slag are not infiltrated after 2-20% of carbon material is added;
step two, although the use temperature of the covering slag reaches 1550 ℃ at most, sodium fluoride generated by a slag layer cannot escape from the surface of the covering slag due to the covering of a covering slag sintering layer and a powder slag layer at high temperature, and the covering slag realizes the control of casting blank cooling by forming gunite to change heat transfer in the casting blank cooling process of a crystallizer;
step three, the casting powder undergoes a thermal process of firstly heating and then cooling, so that a three-layer structure of a slag layer, a sintering layer and a powder slag layer is formed on the surface of a casting blank, and as the powder slag of the casting powder has large dust, and in order to meet the requirement of automatic slag addition, the casting powder firstly uniformly mixes powder slag, water and a binder to prepare slurry, and then the formed slurry is prepared into a hollow granular slag product through high-temperature spray granulation;
step four, water can be rapidly evaporated in the spray granulation process, sodium fluoride and cyanide dissolved in the water can be separated out to the surface of the hollow particle protective slag, the blast furnace slag solid waste and the SPL hazardous waste are converted into production raw materials of the protective slag, the sodium fluoride and the calcium silicate are converted into the gunite by utilizing the heat of steel continuous casting in the using process of the protective slag, and the solid waste treatment is realized without extra energy and reagents.
2. The method for preparing the continuous casting mold flux by using the electrolytic aluminum waste residue, the waste water and the blast furnace slag according to claim 1, wherein the common process of steel smelting is first iron making and then steel making, and a large amount of high slag is generated by the blast furnace iron making.
3. The method for preparing the continuous casting mold flux by using the electrolytic aluminum waste residue, the waste water and the blast furnace slag according to claim 1, wherein 97% of steel produced by converter steelmaking is produced by a continuous casting mode.
4. The method for preparing the continuous casting mold flux by using the electrolytic aluminum waste residue, the waste water and the blast furnace slag according to claim 1, wherein the continuous casting mold flux has five functions of lubricating a casting blank, controlling heat transfer, preventing secondary oxidation of molten steel, absorbing molten steel inclusions and insulating heat as a key functional material of the continuous casting blank.
5. The method for preparing continuous casting mold flux using electrolytic aluminum waste residue, wastewater, blast furnace slag according to claim 1, wherein SPL can provide fluorine, sodium, carbon, aluminum elements required for mold flux in view of element composition.
6. The method for preparing continuous casting mold flux by using the electrolytic aluminum waste residue, the waste water and the blast furnace slag according to claim 1, wherein the blast furnace slag can provide calcium, silicon and aluminum elements required by the mold flux.
7. The method for preparing continuous casting mold flux from electrolytic aluminum waste residue, wastewater and blast furnace slag according to claim 1, wherein the SPL is adjusted by XRF testing the contents of the SPL and the blast furnace slag, the ratio of the wastewater and the blast furnace slag is used for preparing the continuous casting mold flux, and the XRF is used for verifying the component contents of the mold flux.
8. The method for preparing the continuous casting mold flux from the electrolytic aluminum waste residue, the waste water and the blast furnace slag according to claim 7, wherein the XRF is an X-ray fluorescence analyzer.
9. The method for preparing continuous casting mold flux from electrolytic aluminum waste residue, wastewater and blast furnace slag according to claim 1, wherein the SPL and the blast furnace slag can be matched with the similarity of the components of the mold flux, and the fluorine-containing waste water of an electrolytic aluminum plant can be used as a water source of the mold flux slurry by using the characteristics of the mold flux production process.
10. The method for preparing continuous casting mold flux using electrolytic aluminum waste residue, wastewater, blast furnace slag according to claim 1, wherein fluoride dissolved in water is precipitated to the mold flux by high temperature granulation, and the dangerous solid waste is converted into a product using heat of continuous casting steel.
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