CN110016565B - Method for preparing ferro-silicon-aluminum alloy by feeding hollow electrode with waste refractory material as raw material - Google Patents

Method for preparing ferro-silicon-aluminum alloy by feeding hollow electrode with waste refractory material as raw material Download PDF

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CN110016565B
CN110016565B CN201910404104.1A CN201910404104A CN110016565B CN 110016565 B CN110016565 B CN 110016565B CN 201910404104 A CN201910404104 A CN 201910404104A CN 110016565 B CN110016565 B CN 110016565B
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waste
silicon
aluminum
refractory material
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CN110016565A (en
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罗洪杰
吴林丽
徐建荣
张志刚
刘宜汉
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Northeastern University China
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/06—Deoxidising, e.g. killing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B21/00—Obtaining aluminium
    • C22B21/0007—Preliminary treatment of ores or scrap or any other metal source
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B21/00—Obtaining aluminium
    • C22B21/0038—Obtaining aluminium by other processes
    • C22B21/0069—Obtaining aluminium by other processes from scrap, skimmings or any secondary source aluminium, e.g. recovery of alloy constituents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/20—Obtaining alkaline earth metals or magnesium
    • C22B26/22—Obtaining magnesium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001—Dry processes
    • 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
    • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
    • Y02P10/134—Reduction of greenhouse gas [GHG] emissions by avoiding CO2, e.g. using hydrogen
    • 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

Abstract

The invention provides a method for preparing an aluminum-silicon-iron alloy by feeding a hollow electrode by taking a waste refractory material as a raw material, taking a waste cathode carbon block of an aluminum electrolytic cell as a reducing agent, taking fly ash as an additive to adjust the aluminum content in the raw material, taking diatomite waste residue as an additive to adjust the silicon content in the raw material, and reducing the material mainly comprising aluminum oxide and silicon oxide at a high temperature in an electric arc furnace to prepare the aluminum-silicon-iron alloy with a certain component; the hollow electrode is adopted to convey the powdery material, so that the whole smelting process of the electric arc furnace can be enhanced, the reduction of oxides and the volatilization of fluorides are promoted, particularly the decomposition of toxic cyanide substances and the volatilization and recovery of fluorides, chlorides and alkali metals in the material are accelerated, the production efficiency is improved, the production cost is reduced, and the comprehensive utilization of various hazardous wastes and solid wastes is realized in the same process.

Description

Method for preparing ferro-silicon-aluminum alloy by feeding hollow electrode with waste refractory material as raw material
Technical Field
The invention relates to the field of electric metallurgy, in particular to a method for preparing an aluminum-silicon-iron alloy by feeding a hollow electrode by taking a waste refractory material as a raw material.
Background
The production method of ferro-silicon-aluminum is mainly divided into a metal melting and proportioning method and an electric heating reduction method. The metal melting method is to mix pure metal aluminum, silicon and iron according to a certain proportion in a melting state to form an alloy; the electrothermal reduction method is to prepare the alloy by taking oxides containing aluminum, silicon and iron as raw materials and carbonaceous materials as reducing agents and carrying out reduction smelting in an electric arc furnace. The metal melting and matching method has the problems of reheating of pure metal, secondary burning loss, high production cost and the like. The electrothermal reduction method also has the problems of pure mineral raw material shortage, poor economical efficiency of the production process and the like.
The aluminum electrolysis cell is the main equipment for producing the metal aluminum. After the aluminum electrolytic cell is damaged and overhauled, a large amount of overhauling slag of the aluminum electrolytic cell can be generated. The overhaul slag comprises a cathode carbon block, cathode paste, refractory bricks, insulating bricks, impermeable materials, an insulating plate and the like. The overhaul slag can be further divided into two main parts, namely a waste refractory material lining (anti-seepage material, refractory brick and insulating brick) corroded by fluoride electrolyte and a waste cathode carbon block (cathode carbon block and cathode paste), wherein the mass ratio of the waste cathode carbon block to the waste refractory material accounts for 50 percent respectively. At present, 5-10kg of waste cathode carbon blocks and 5-10kg of waste refractory materials are produced per ton of metallic aluminum produced.
The waste refractory material is mainly waste dry type impermeable material positioned at the lower part of the cathode carbon block, and accounts for about 90 percent of the waste refractory material. The main components of the raw material of the dry type impermeable material are alumina and silicon oxide, and the main component of the waste impermeable material after being eroded by the electrolyte is nepheline (NaAlSiO)4) Or albite (NaAlSi)3O8) Besides, it also contains 10-15% of fluoride electrolyte, iron oxide, calcium oxide, aluminium carbide and other oxide and carbide impurities and small quantity of aluminium, silicon, aluminium-silicon-iron and other metals and alloys. These waste refractories are also regarded as hazardous waste because of the high amount of fluoride present. At present, the waste refractory materials generated during the overhaul of the aluminum electrolytic cell are not effectively recycled and treated, and are generally treated mainly by landfill. Because the waste refractory material contains a lot of soluble substances such as electrolyte fluoride, sodium oxide and the like, the long-term stacking can cause great harm to underground water and the surrounding environment.
The main component of the waste cathode carbon block is a carbonaceous material, and the most component except the carbonaceous material is an electrolyte. The electrolyte components in the waste cathode carbon block mainly comprise NaF and Na3AlF6、Na5Al3F14And CaF2And the like. The carbon content in the waste cathode carbon block for aluminum electrolysis is generally 60-70%, and the electrolyte component content is 15-25%. In addition, 4% -8% of alkali gold exists in the aluminum electrolysis waste cathodeThe genus is mainly metallic sodium. When potassium salt is present in the electrolyte component, potassium metal is also present in the spent cathode carbon block. Besides the three main components, the waste cathode carbon block also contains a small amount of carbide, nitride, oxide and cyanide, wherein the content of cyanide accounts for 0.1-0.2% of the total mass of the waste cathode carbon. The NaCN, complex cyanides and fluorides in the spent cathode carbon block are major environmental hazards. Cyanide and most fluoride are dissolved in water, and the waste cathode carbon blocks accumulated for a long time pollute underground water and surface water and cause serious pollution to the environment. The treatment of the waste cathode carbon block of the aluminum electrolytic cell is divided into two types, one type is a treatment technology, namely, the waste cathode carbon block material is buried after being innoxious or is utilized by other industries, such as a high-temperature hydrolysis technology, a combustion power generation technology, a slag former for manufacturing a high-speed rail industry, a fuel and a mineral raw material used for a cement industry, an inert material which can be buried and the like; the other is a recycling technology, which mainly recycles fluoride and carbon in the waste cathode carbon block, such as wet leaching to recycle fluoride, serving as an additive of a cathode carbon block and an anode carbon block, separating fluoride electrolyte and the carbon block by a flotation method, and the like, but the existing treatment of the waste cathode carbon block has not reached the industrial level yet.
Each ton of coal burned will produce 0.15-0.3 ton of fly ash, and coal with high ash content will produce 0.4-0.5 ton of fly ash at most. At present, the quantity of the fly ash generated in China every year reaches more than 6 hundred million tons. A small amount of high-alumina fly ash can be used for extracting alumina, while a large amount of low-alumina fly ash is mainly used for producing various building materials, such as cement admixtures, concrete additives and building material deep-processing products, and refractory and heat-insulating materials by extracting floating beads from fly ash, but the utilization problem of the fly ash cannot be fundamentally solved by the methods. In addition, the added value of the produced building materials is low, and utilization enterprises of the building materials are required to be close to large cities with a large number of people, so that the utilization method is mainly adopted in east provinces of China. The fly ash distributed in Shanxi, inner Mongolia, Ningxia, Shaanxi, Gansu and Xinjiang is not effectively utilized, and most of the fly ash is still treated in a stacking and burying manner.
The rollers of aluminum processing enterprises need to be cooled and lubricated by rolling oil in the production process, the rolling oil needs to be filtered after being used for a period of time, and the filtering medium adopts diatomite materials. In the aluminum material rolling process, the aluminum material is soft, and the roller has less abrasion, so impurities in the rolling oil mainly come from abrasion powder of the aluminum material. When the filtering precision of the diatomite does not reach the use standard of the rolling oil after the diatomite is used for a certain time, the diatomite needs to be replaced periodically. The replaced oil-containing waste diatomite is regarded as dangerous waste, so that the risk of environmental pollution is avoided, and meanwhile, the resource is greatly wasted. The main components of diatomite in China are silicon dioxide, aluminum oxide and ferric oxide. At present, diatomite waste residues generated by filtering rolling oil in an aluminum processing plant mainly contain rolling oil and aluminum powder, wherein the rolling oil can be deoiled by using an oil removing machine, the deoiled oil can be used for producing kerosene, and the diatomite waste residues are not effectively treated.
From the above analysis it can be seen that: hazardous wastes and solid wastes generated in the existing electrolytic aluminum and aluminum processing and power industry are respectively treated, most of the hazardous wastes are in a harmless treatment stage, and effective resource utilization is in a research stage, so that the problem of environmental pollution of the solid wastes is not fundamentally solved.
Disclosure of Invention
The invention provides a method for preparing ferro-silicon-aluminum alloy by feeding a hollow electrode by taking a waste refractory material as a raw material, taking a waste cathode carbon block of an aluminum electrolytic cell as a reducing agent, taking fly ash as an additive to adjust the aluminum content and the silicon content in the raw material, and reducing the material mainly comprising aluminum oxide and silicon oxide at high temperature in an electric arc furnace to prepare the ferro-silicon-aluminum alloy with a certain component; the decomposition of cyanide in the waste cathode carbon block and the volatilization and recovery of fluoride and alkali metal in the material are realized in the high-temperature reduction process, and the comprehensive utilization of various dangerous wastes and solid wastes is realized in the same process. In order to achieve the purpose, the invention adopts the following technical scheme:
the method for preparing the ferro-silicon-aluminum alloy by feeding the hollow electrode by taking the waste refractory material as the raw material comprises the following steps:
step 1, respectively preparing a waste refractory material, a waste cathode carbon block and fly ash in overhaul residues of an aluminum electrolytic cell into powder;
step 2, determining the use amounts of the waste refractory material, the fly ash and the waste cathode carbon block according to the components of the target ferro-silicon-aluminum alloy, and reducing Al in the waste refractory material by using fixed carbon contained in the waste cathode carbon block as a reducing agent according to a stoichiometric ratio2O3、SiO2The amount of metal aluminum and silicon generated by the oxide is calculated, and then the waste cathode carbon block is used for reducing Al in the fly ash2O3、SiO2The amount of the metal aluminum and the silicon obtained by the oxide is adjusted by the amount of the metal aluminum and the silicon obtained by reducing the waste refractory material by using the amount of the metal aluminum and the silicon obtained by reducing the fly ash, so that the components of the aluminum and the silicon in the prepared aluminum-silicon-iron alloy and the use amounts of the waste refractory material, the fly ash and the waste cathode carbon block can be obtained; putting the waste refractory material, the fly ash and the waste cathode carbon block powder together into a mixer to be uniformly mixed;
step 3, starting the electric arc furnace, gradually increasing the temperature in the furnace, wherein the electrode adopted by the electric arc furnace is a hollow electrode, a hollow channel in the middle of the electrode is connected with a compressed gas pipeline for conveying the powdery material, when the temperature of a bottom arc zone is 1700-plus 2100 ℃, the powdery material is conveyed to an electric arc reaction zone through the hollow channel by taking the compressed gas as a carrier, and when the melting process reaches 2-6h, the formed aluminum-silicon-iron alloy melt is discharged from the bottom of the electric arc furnace and is refined outside the furnace, so that the aluminum-silicon-iron alloy can be obtained, can be used as a steelmaking deoxidizer and a magnesium-smelting reducer, and the refined slag is returned to the batching process for continuous use;
and 4, leaching the ash collected from the top of the electric arc furnace, filtering, wherein the leaching temperature is 20-100 ℃, the liquid-solid ratio in the leaching process is 2-10: 1, the leaching time is 0.5-3 h, filtering is performed after leaching, sodium carbonate is recovered from the leachate through evaporation, leached slag is dried and then melted at high temperature, the melting temperature is not lower than 1000 ℃, so that fluoride is separated from oxide, the recovered fluoride electrolyte is returned to an electrolytic bath for use, and slag phase oxide is returned to an electric arc furnace raw material batching workshop to be used as a raw material for smelting ferro-aluminium in the electric arc furnace.
The waste refractory material comprises the following components in percentage by mass: na (Na)2O 5～30％，Al2O315～50％，SiO210～50％，Fe2O3≤10％，K2O≤3％，CaO≤3％，F≤10％。
The waste cathode carbon block comprises the following components in percentage by mass: 60-80% of C and Al2O30-3%, 4-10% of Na, 10-20% of fluoride electrolyte, wherein the fluoride electrolyte mainly comprises cryolite, sodium fluoride and calcium fluoride, and can also contain lithium fluoride and potassium fluoride.
The fly ash comprises the following components in percentage by mass: al (Al)2O315～50％，SiO230～50％，Fe2O30～10％，CaO≤5％，MgO≤5％，Na2O≤3％，K2O≤3％，TiO2Less than or equal to 3 percent and the content of other single metal oxides is less than 1 percent.
The dry pulp powder comprises the following components in percentage by mass: the calcium lignosulphonate is more than or equal to 90 percent, and the dry basis moisture is more than or equal to 8 percent.
In the step 1, the particle sizes of the waste refractory material, the waste cathode carbon block, the fly ash and the diatomite waste residue powder are all smaller than 100 meshes.
And 3, the diameter of the hollow channel in the middle of the electrode is 20mm-200 mm.
In the step 3, the compressed gas is one of argon, air and carbon monoxide.
And 3, controlling the pressure of the compressed gas to be between 0.1 and 0.8 MPa.
In the step 3, the refining agent used for the external refining contains sodium chloride, potassium chloride and cryolite, wherein the proportion of each component is 30-60 percent of sodium chloride, less than or equal to 30 percent of potassium chloride and less than or equal to 30 percent of cryolite; the refining temperature is 900-1500 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1. the existing waste refractory materials, waste cathode carbon blocks and fly ash are treated separately, namely, a plurality of processes and a plurality of treatment systems are adopted. Among them, the treatment of the waste refractory materials is generally to landfill or to carry out harmless treatment and then to stockpile. The treatment process of the waste cathode carbon block is divided into a wet method and a fire method, the wet method is mainly used, strong acid or strong alkali is adopted for leaching, fluoride is converted into soluble hydrogen fluoride or sodium fluoride to be separated from a carbonaceous material, a large amount of acid-containing or alkali-containing wastewater is generated in the treatment process, and secondary pollution is easily caused. The invention relates to an integrated treatment technology developed aiming at various dangerous wastes and solid wastes, wherein a waste refractory material, a waste cathode carbon block and fly ash are all treated and recovered in an electrothermal carbon reduction process. The pyrolysis of main toxic substance cyanide has not only been realized at the carbothermic reduction in-process, has realized the high temperature volatilization separation of fluoride in useless refractory material and the useless negative pole charcoal piece moreover, and the metal oxide in useless refractory material and the useless negative pole charcoal piece is reduced and gets into the ferro-silicon-aluminum alloy in the processing procedure, and whole process does not have the formation of waste residue and waste water, is a green treatment process.
2. The treatment process mainly aims at harmlessness and reduction when treating hazardous wastes such as waste refractory materials, waste cathode carbon blocks and the like, realizes resource utilization of wastes while harmlessness and reduction are realized, namely, fixed carbon in the waste cathode carbon blocks is used as a reducing agent to reduce alumina, silica, iron oxide and the like in the waste refractory materials, diatomite waste residues and fly ash in a metal form, and simultaneously, fluoride and alkali metal are recycled, so that the waste is treated by the waste, and the whole process is closed cycle.
3. The method uses secondary waste refractory materials as raw materials and uses fly ash as an additive to adjust the aluminum content and the silicon content in the raw materials, and the batching mode not only utilizes various wastes, but also is easy to prepare the Al-Si-Fe alloy with various components so as to adapt to the smelting process of an electric arc furnace, so that the smelting process and the alloy components are easy to regulate and control, the production cost is reduced, and conditions are created for subsequent treatment.
4. The hollow electrode is adopted to convey the powdery material, so that the whole smelting process of the electric arc furnace can be strengthened, the reduction of oxides and the volatilization of fluorides are promoted, particularly the decomposition of toxic cyanide is accelerated, the production efficiency is improved, and the production cost is reduced.
Drawings
FIG. 1 is a process flow chart of the method for preparing the ferro-silicon-aluminum alloy by feeding the hollow electrode with the waste refractory material as the raw material.
Detailed Description
The technical scheme of the invention is explained in detail by taking the following waste materials as examples.
Table 1 shows the main components of a waste refractory. The composition and content of the waste refractory materials vary from enterprise to enterprise due to differences in the electrolysis process and electrolyte composition, as well as the life of the cell.
TABLE 1 Main Components of waste refractory
Figure BDA0002060227870000061
Table 2 shows the main components of a waste cathode carbon block, and the components and contents of the waste cathode carbon block are different between different enterprises due to the difference in the electrolysis process and the composition of the electrolyte, and the difference in the service life of the electrolytic cell.
TABLE 2 Main Components of waste cathode carbon blocks
Figure BDA0002060227870000062
Table 3 shows the main components of a low-alumina fly ash.
TABLE 3 Main Components of Low-aluminum fly ash
Figure BDA0002060227870000063
Figure BDA0002060227870000071
Example 1
The method for preparing the ferro-silicon-aluminum alloy by feeding the hollow electrode by taking the waste refractory material as the raw material comprises the following steps:
step 1, respectively preparing a waste refractory material, a waste cathode carbon block and fly ash in the overhaul residues of the aluminum electrolytic cell into powder with the granularity of 100 meshes;
step 2, according to the components of the target ferro-silicon-aluminum alloy: the method comprises the following steps of (1) calculating the mass of a waste refractory material, a waste cathode carbon block and fly ash required for reducing metal oxides by taking fixed carbon contained in the waste cathode carbon block as a reducing agent according to a stoichiometric ratio, wherein the mass ratio of the waste refractory material, the waste cathode carbon block and the fly ash is 1:6:4, and uniformly mixing the waste refractory material, the waste cathode carbon block and the fly ash in a mixer;
step 3, starting the electric arc furnace, gradually increasing the temperature in the furnace, wherein the electrode adopted by the electric arc furnace is a hollow electrode, a hollow channel in the middle of the electrode is connected with a compressed gas pipeline for conveying the powdery material, when the temperature of a bottom arc zone is 2100 ℃, the powdery material is conveyed to an electric arc reaction zone through the hollow channel by taking compressed air as a carrier, and when the smelting process reaches 6 hours, the formed aluminum-silicon-iron alloy melt is discharged from the bottom of the electric arc furnace and is refined outside the furnace; the diameter of the hollow channel is 200mm, the pressure is controlled to be 0.1MPa, the used refining agent contains sodium chloride, potassium chloride and cryolite, and the proportion range of each component is 50% of sodium chloride, 40% of potassium chloride and 10% of cryolite; the refining temperature is 1500 ℃, so that the ferro-silicon-aluminum alloy can be obtained, the alloy can be used as a steel-making deoxidizer and a magnesium-making reducer, and the refining slag returns to the batching process for continuous use;
step 4, leaching the soot collected from the top of the electric arc furnace by water and filtering, wherein the leaching temperature is 95 ℃, the liquid-solid ratio in the leaching process is 10:1, the leaching time is 0.5h, filtering is carried out after leaching, and the sodium carbonate is recovered from the leaching solution through evaporation; and (3) drying the leached slag, then melting at high temperature of 1200 ℃, separating fluoride from oxide, returning the recovered fluoride electrolyte to an electrolytic cell for use, and returning slag phase oxide to an electric arc furnace raw material batching plant as a raw material for smelting ferro-silicon-aluminum by the electric arc furnace.
Example 2
The method for preparing the ferro-silicon-aluminum alloy by feeding the hollow electrode by taking the waste refractory material as the raw material comprises the following steps:
step 1, respectively preparing a waste refractory material, a waste cathode carbon block and fly ash in the overhaul residues of the aluminum electrolytic cell into powder with the granularity of 100 meshes;
step 2, according to the components of the target ferro-silicon-aluminum alloy: 27 percent of aluminum, 63 percent of silicon and the balance of iron, calcium, titanium and other trace metals; calculating the mass of the waste refractory material, the fly ash and the waste cathode carbon block required for reducing the metal oxide by taking fixed carbon contained in the waste cathode carbon block as a reducing agent according to a stoichiometric ratio to obtain the mass ratio of the waste refractory material, the fly ash and the waste cathode carbon block of 1:3: 2; putting the waste refractory material, the waste cathode carbon block and the fly ash into a mixer together and uniformly mixing;
step 3, starting the electric arc furnace, gradually increasing the temperature in the furnace, wherein the electrode adopted by the electric arc furnace is a hollow electrode, a hollow channel in the middle of the electrode is connected with a compressed gas pipeline for conveying the powdery material, when the temperature of a bottom arc zone is 19000 ℃, the powdery material is conveyed to an electric arc reaction zone through the hollow channel by taking compressed argon as a carrier, and when the smelting process reaches 4 hours, the formed aluminum-silicon-iron alloy melt is discharged from the bottom of the electric arc furnace and is refined outside the furnace; the diameter of the hollow channel is 100mm, and the pressure is controlled to be 0.4 MPa; the refining agent contains sodium chloride, potassium chloride and cryolite, and the proportion ranges of the components are 40% of sodium chloride, 40% of potassium chloride and 20% of cryolite; refining at 1200 ℃ to obtain the ferro-silicon-aluminum alloy; the alloy can be used as a steel-making deoxidizer and a magnesium-making reducer, and refining slag returns to the batching process for continuous use;
and 4, leaching the soot collected from the top of the electric arc furnace, filtering, wherein the leaching temperature is 60 ℃, the liquid-solid ratio in the leaching process is 6:1, the leaching time is 1.5h, filtering is carried out after leaching, sodium carbonate is recovered from the leaching solution through evaporation, leaching slag is dried and then melted at high temperature, the melting temperature is 1100 ℃, so that fluoride is separated from oxide, the recovered fluoride electrolyte is returned to an electrolytic bath for use, and slag phase oxide is returned to a raw material batching plant of the electric arc furnace to be used as a raw material for smelting aluminum silicon iron by the electric arc furnace.
Example 3
The method for preparing the ferro-silicon-aluminum alloy by feeding the hollow electrode by taking the waste refractory material as the raw material comprises the following steps:
step 1, respectively preparing a waste refractory material, a waste cathode carbon block and fly ash in the overhaul residues of the aluminum electrolytic cell into powder with the granularity of 100 meshes;
step 2, according to the components of the target ferro-silicon-aluminum alloy: the aluminum content is 31 percent, the silicon content is 58 percent, and the rest is iron, calcium, titanium and other trace metals; calculating the mass of the waste refractory material, the fly ash and the waste cathode carbon block required for reducing the metal oxide by taking fixed carbon contained in the waste cathode carbon block as a reducing agent according to a stoichiometric ratio to obtain the mass ratio of the waste refractory material, the fly ash and the waste cathode carbon block of 1:1: 1; putting the waste refractory material, the waste cathode carbon block and the fly ash into a mixer together and uniformly mixing;
step 3, starting the electric arc furnace, gradually increasing the temperature in the furnace, wherein the electrode adopted by the electric arc furnace is a hollow electrode, a hollow channel in the middle of the electrode is connected with a compressed gas pipeline for conveying the powdery material, when the temperature of a bottom arc zone is 1700 ℃, the powdery material is conveyed to an electric arc reaction zone through the hollow channel by taking compressed carbon monoxide as a carrier, and when the smelting process reaches 2 hours, the formed aluminum-silicon-iron alloy melt is discharged from the bottom of the electric arc furnace and is refined outside the furnace; the diameter of the hollow channel is 20mm, and the pressure is controlled to be 0.8 MPa; the refining agent contains sodium chloride, potassium chloride and cryolite, and the proportion ranges of the components are 60% of sodium chloride, 10% of potassium chloride and 30% of cryolite; the refining temperature is 900 ℃, the ferro-silicon-aluminum alloy can be obtained and can be used as a steel-making deoxidizer and a magnesium-making reducer, and the refining slag returns to the batching process for continuous use;
and 4, leaching the soot collected from the top of the electric arc furnace by water and filtering, wherein the leaching temperature is 20 ℃, the liquid-solid ratio in the leaching process is 2:1, the leaching time is 3 hours, filtering is carried out after leaching, sodium carbonate is recovered from the leaching solution through evaporation, leaching slag is dried and then melted at high temperature, the melting temperature is 1000 ℃, so that fluoride is separated from oxide, the recovered fluoride electrolyte is returned to an electrolytic bath for use, and slag phase oxide is returned to a raw material batching workshop of the electric arc furnace to be used as a raw material for smelting ferro-aluminium in the electric arc furnace.

Claims (9)

1. The method for preparing the ferro-silicon-aluminum alloy by feeding the hollow electrode by taking the waste refractory material as the raw material is characterized by comprising the following steps of:
step 1, respectively preparing a waste refractory material, a waste cathode carbon block and fly ash in overhaul residues of an aluminum electrolytic cell into powder;
step 2, determining the use amounts of the waste refractory material, the fly ash and the waste cathode carbon block according to the components of the target ferro-silicon-aluminum alloy, and reducing Al in the waste refractory material by using fixed carbon contained in the waste cathode carbon block as a reducing agent according to a stoichiometric ratio2O3、SiO2The amount of metal aluminum and silicon generated by the oxide is calculated, and then the waste cathode carbon block is used for reducing Al in the fly ash2O3、SiO2The amount of the metal aluminum and the silicon obtained by the oxide is adjusted by the amount of the metal aluminum and the silicon obtained by reducing the waste refractory material by using the amount of the metal aluminum and the silicon obtained by reducing the fly ash, so that the components of the aluminum and the silicon in the prepared aluminum-silicon-iron alloy and the use amounts of the waste refractory material, the fly ash and the waste cathode carbon block can be obtained; putting the waste refractory material, the fly ash and the waste cathode carbon block powder together into a mixer to be uniformly mixed;
step 3, starting the electric arc furnace, gradually increasing the temperature in the furnace, wherein the electrode adopted by the electric arc furnace is a hollow electrode, a hollow channel in the middle of the electrode is connected with a compressed gas pipeline for conveying the powdery material, when the temperature of a bottom arc zone is 1700-plus 2100 ℃, the powdery material is conveyed to an electric arc reaction zone through the hollow channel by taking the compressed gas as a carrier, and when the melting process reaches 2-6h, the formed aluminum-silicon-iron alloy melt is discharged from the bottom of the electric arc furnace and is refined outside the furnace, so that the aluminum-silicon-iron alloy can be obtained, can be used as a steelmaking deoxidizer and a magnesium-smelting reducer, and the refined slag is returned to the batching process for continuous use;
and 4, leaching the ash collected from the top of the electric arc furnace, filtering, wherein the leaching temperature is 20-100 ℃, the liquid-solid ratio in the leaching process is 2-10: 1, the leaching time is 0.5-3 h, filtering is performed after leaching, sodium carbonate is recovered from the leachate through evaporation, leached slag is dried and then melted at high temperature, the melting temperature is not lower than 1000 ℃, so that fluoride is separated from oxide, the recovered fluoride electrolyte is returned to an electrolytic bath for use, and slag phase oxide is returned to an electric arc furnace raw material batching workshop to be used as a raw material for smelting ferro-aluminium in the electric arc furnace.
2. The method of claim 1The method for preparing the ferro-silicon-aluminum alloy by feeding the hollow electrode by taking the waste refractory material as the raw material is characterized in that the waste refractory material comprises the following components in percentage by mass: na (Na)2O 5～30％，Al2O315～50％，SiO210～50％，Fe2O3≤10％，K2O≤3％，CaO≤3％，F≤10％。
3. The method for preparing the ferro-silicon-aluminum alloy by feeding the hollow electrode by taking the waste refractory material as the raw material according to claim 1, wherein the waste cathode carbon block comprises the following components in percentage by mass: 60-80% of C and Al2O30-3%, Na 4-10%, and 10-20% of fluoride electrolyte.
4. The method for preparing the ferro-silicon-aluminum alloy by feeding the hollow electrode by taking the waste refractory material as the raw material according to claim 1, wherein the fly ash comprises the following components in percentage by mass: al (Al)2O315～50％，SiO230～50％，Fe2O3≤10％，CaO≤5％，MgO≤5％，Na2O≤3％，K2O≤3％，TiO2Less than or equal to 3 percent and the content of other single metal oxides is less than 1 percent.
5. The method for preparing the sendust alloy by feeding the hollow electrode with the waste refractory material as the raw material according to claim 1, wherein in the step 1, the particle sizes of the waste refractory material, the waste cathode carbon block and the fly ash are all less than 100 meshes.
6. The method for preparing Al-Si-Fe alloy by feeding hollow electrode with waste refractory material as raw material according to claim 1, wherein in step 3, the diameter of the hollow channel in the middle of the electrode is 20mm-200 mm.
7. The method for preparing sendust according to claim 1, wherein in step 3, the compressed gas is one of argon, air and carbon monoxide.
8. The method for producing AlSiFe alloy from hollow electrode feed materials made of waste refractory materials as claimed in claim 1, wherein in step 3, the pressure of said compressed gas is controlled to be between 0.1-0.8 MPa.
9. The method for preparing the sendust alloy by feeding the hollow electrode by using the waste refractory materials as the raw materials according to claim 1, wherein in the step 3, the refining agent used for the external refining contains 30-60% of sodium chloride, 30% or less of potassium chloride and 30% or less of cryolite, and the proportion of each component is 30-60%; the refining temperature is 900-1500 ℃.
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