CN110004300B - Method for preparing ferrosilicon alloy by using aluminum ash as raw material through plasma jet feeding - Google Patents

Method for preparing ferrosilicon alloy by using aluminum ash as raw material through plasma jet feeding Download PDF

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CN110004300B
CN110004300B CN201910403084.6A CN201910403084A CN110004300B CN 110004300 B CN110004300 B CN 110004300B CN 201910403084 A CN201910403084 A CN 201910403084A CN 110004300 B CN110004300 B CN 110004300B
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aluminum
ash
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aluminum ash
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CN110004300A (en
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罗洪杰
王耀武
吴林丽
高国磊
曲杨
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Northeastern University China
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01DCOMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00Halides of sodium, potassium or alkali metals in general
    • C01D3/04Chlorides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01DCOMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D7/00Carbonates of sodium, potassium or alkali metals in general
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21CPROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04Removing impurities by adding a treating agent
    • C21C7/06Deoxidising, e.g. killing
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B21/00Obtaining aluminium
    • C22B21/02Obtaining aluminium with reducing
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00General methods of reducing to metals
    • C22B5/02Dry methods smelting of sulfides or formation of mattes
    • C22B5/10Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working 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
    • C22B7/001Dry processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making alloys
    • C22C1/02Making alloys by melting
    • C22C1/026Alloys based on aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making alloys
    • C22C1/06Making alloys with the use of special agents for refining or deoxidising
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The invention provides a method for preparing ferrosilicon alloy by taking aluminum ash as a raw material and carrying out plasma jet feeding, wherein secondary aluminum ash is taken as a raw material, waste cathode carbon blocks of an aluminum electrolytic cell are taken as a reducing agent, fly ash is taken as an additive to adjust the aluminum content in the raw material, diatomite waste residue is taken as an additive to adjust the silicon content in the raw material, and the material mainly comprising aluminum oxide and silicon oxide is reduced at high temperature in an electric arc furnace to prepare the ferrosilicon alloy with a certain component; the plasma flame flow is adopted to convey the powdery material, so that the reaction temperature can be increased by heating the material, the reduction of oxides and the volatilization of fluorides are accelerated, the decomposition of aluminum nitride in aluminum ash and the decomposition of cyanides in waste cathode carbon blocks are realized particularly in the high-temperature reduction process, and the volatilization and recovery of fluorides, chlorides and alkali metals in the material are realized, the high-temperature reaction process of the whole electric arc furnace smelting is strengthened, and the production efficiency is improved. The comprehensive utilization of various hazardous wastes and solid wastes is realized in the same process.

Description

Method for preparing ferrosilicon alloy by using aluminum ash as raw material through plasma jet feeding
Technical Field
The invention relates to the field of electric metallurgy, in particular to a method for preparing ferrosilicon alloy by taking aluminum ash as a raw material and carrying out plasma jet feeding.
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.
A large amount of aluminum ash is generated in the aluminum electrolysis, aluminum processing and scrap aluminum remelting recovery processes. The current methods for treating these aluminum ashes are mainly: after screening the aluminum ash, remelting the massive aluminum ash to obtain metal aluminum; or the aluminum ash is treated by an ash frying machine to recover the metal aluminum, and the aluminum ash left after screening or treatment by the ash frying machine is generally called secondary aluminum ash, and the secondary aluminum ash is mainly treated in a landfill or stockpiling mode at present. The aluminum ash generated in the aluminum smelting and processing process usually contains 50-80% of metallic aluminum, and after the conventional recovery treatment, the residual secondary aluminum ash mainly contains metallic aluminum, aluminum oxide and aluminum nitride, wherein the main components of the secondary aluminum ash contain 5-10% of metallic aluminum, more than 40% of aluminum oxide and 10-25% of aluminum nitride. According to different refining modes of manufacturers, the aluminum ash also contains 5-10% of fluoride and chloride. As a large amount of aluminum nitride contained in the aluminum ash can generate ammonia when meeting water, and chlorides and fluorides contained in the aluminum ash can also be dissolved in water, the aluminum ash is listed in the name of hazardous wastes by the ministry of environmental protection in 2016. At present, the method for treating the secondary aluminum ash not only does not utilize valuable resources in the secondary aluminum ash, but also has huge ecological risks.
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 of waste cathode carbon blocks (cathode carbon blocks and cathode paste) and waste refractory material linings (refractory bricks, insulating bricks and impermeable materials) eroded by fluoride electrolyte, wherein the waste cathode carbon blocks and the waste refractory materials are made of the sameThe quantitative proportions are approximately 50% each. 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 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 metal, mainly metallic sodium, is present in the aluminum electrolysis spent cathodes. 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 an aluminum-silicon-iron alloy by taking aluminum ash as a raw material and carrying out plasma jet feeding, wherein secondary aluminum ash is taken as a raw material, waste cathode carbon blocks of an aluminum electrolytic cell are taken as a reducing agent, fly ash is taken as an additive to adjust the aluminum content in the raw material, diatomite waste residue is taken as an additive to adjust the silicon content in the raw material, and the material mainly comprising aluminum oxide and silicon oxide is reduced at high temperature in an electric arc furnace to prepare the aluminum-silicon-iron alloy with a certain component; the decomposition of aluminum nitride in aluminum ash and the decomposition of cyanide in waste cathode carbon blocks are realized in the high-temperature reduction process, and the volatilization and recovery of fluoride, chloride and alkali metal in materials are realized, so that 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 plasma jet feeding process of preparing Al-Si-Fe alloy with aluminum ash as material includes the following steps:
step 1, respectively preparing aluminum ash, waste cathode carbon blocks in overhaul residues of an aluminum electrolytic cell, fly ash and diatomite waste residues into powder;
step 2, determining the use amounts of aluminum ash, waste cathode carbon blocks, fly ash and diatomite waste residues according to the components of the target ferro-silicon-aluminum alloy, and reducing Al in secondary aluminum ash by using fixed carbon contained in the waste cathode carbon blocks as a reducing agent according to a stoichiometric ratio2O3、SiO2The amount of metal aluminum and silicon generated by oxides is calculated, and then the Al of the waste residue of fly ash and diatomite reduced by the waste cathode carbon block is calculated2O3、SiO2The amount of the metal aluminum and silicon obtained by the oxide is adjusted by the amount of the metal aluminum and silicon obtained by reducing the fly ash and the diatomite waste residue, so that the components of the aluminum and the silicon in the prepared aluminum-silicon-iron alloy and the use amounts of the aluminum ash, the fly ash, the diatomite waste residue and the waste cathode carbon block are obtained; putting the secondary aluminum ash, the waste cathode carbon block, the fly ash and the diatomite waste residue powder into a mixer together for uniformly mixing;
step 3, starting the electric arc furnace and gradually increasing the temperature in the furnace, wherein the electrode adopted by the electric arc furnace is a hollow electrode, and a hollow channel in the middle of the electrode is connected with a flame outflow port of the plasma generator; when the temperature of the bottom arc zone is 1900-; 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 by water, 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 and sodium chloride are recovered from the leachate through evaporation, the leached slag is dried and then melted at high temperature, the melting temperature is higher than 1000 ℃, so that fluoride is separated from oxide, the recovered fluoride electrolyte is returned to an electrolytic cell for use, and the 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 aluminum ash comprises the following components in percentage by mass: al (Al)2O340~80%,AlN≤20%,Al≤10%,SiO2≤5%,Na2O≤5%,Fe2O3Less than or equal to 5 percent, less than or equal to 10 percent of chloride and less than or equal to 10 percent of fluoride.
The waste cathode carbon block comprises the following components in percentage by mass: 60-80% of C and Al2O3Less than or equal to 3 percent, 4-10 percent of Na, 10-20 percent of fluoride electrolyte, wherein the fluoride electrolyte mainly comprises cryolite, sodium fluoride and calcium fluoride, or contains lithium fluoride and potassium fluoride.
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.
The diatomite waste residue comprises the following components in percentage by mass: al (Al)2O3≤5%,SiO280~99%,Fe2O3≤10%。
In the step 1, the granularity of the aluminum ash, the waste cathode carbon block, the fly ash and the diatomite waste residue powder is less than 100 meshes.
And 3, the diameter of the hollow channel in the middle of the electrode is 20mm-200 mm.
And 3, controlling the flow and the flow rate of the plasma flame flow, wherein the temperature of the plasma flame flow is between 300 ℃ and 3000 ℃.
In step 3, the working gas of the plasma generator is one of argon, air and carbon monoxide.
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 aluminum ash, waste cathode carbon blocks, diatomite waste residues and fly ash are treated separately, namely, a plurality of processes and a plurality of treatment systems are adopted. The method comprises the following steps of treating most of aluminum ash by a wet method, reacting aluminum nitride in the aluminum ash with water to generate ammonia gas through the wet method, using waste residues to produce refractory materials, producing a large amount of wastewater containing chlorine, fluorine and ammonia in the treatment process, and incompletely decomposing the aluminum nitride in the waste residues. The treatment process of the waste cathode carbon block also comprises a wet method and a fire method, wherein the wet method is mainly used, the method adopts strong acid or strong alkali for leaching so that fluoride is converted into soluble hydrogen fluoride or sodium fluoride to be separated from a carbonaceous material, and a large amount of acid-containing or alkali-containing wastewater is generated in the treatment process, so that secondary pollution is easily caused. Oil-containing diatomite is mainly extracted at present, and diatomite waste residues formed after oil extraction are mainly stockpiled. The invention relates to an integrated treatment technology developed aiming at various dangerous wastes and solid wastes, wherein aluminum ash, waste cathode carbon blocks, diatomite waste residues and fly ash are all treated and recovered in an electrothermal carbon reduction process. The high-temperature decomposition of main toxic substances, namely aluminum nitride and cyanide, is realized in the carbothermic reduction process, the high-temperature volatilization separation of fluoride in aluminum ash and waste cathode carbon blocks is realized, the metal oxide in the aluminum ash and the waste cathode carbon blocks is reduced to enter the aluminum-silicon-iron alloy in the treatment process, and the whole process is free from generation of waste residues and waste water and is a green and environment-friendly treatment process.
2. The treatment process mainly aims at harmlessness and reduction in the treatment of hazardous wastes such as aluminum ash, waste cathode carbon blocks, diatomite waste residues and the like, realizes resource utilization of wastes while harmlessness and reduction are realized, namely, the fixed carbon in the waste cathode carbon blocks is used as a reducing agent to reduce aluminum oxide, silicon oxide, iron oxide and the like in the aluminum ash, the diatomite waste residues and fly ash in a metal form, and simultaneously, fluoride and alkali metal are recycled, so that the treatment of wastes with wastes is realized, and the whole process is a closed cycle.
3. The secondary aluminum ash is used as a raw material, the fly ash is used as an additive to adjust the aluminum content in the raw material, and the diatomite waste residue is used as an additive to adjust the silicon content in the raw material.
4. The plasma flame flow is adopted to convey the powdery material, so that the reaction temperature can be increased by heating the material, the reduction of oxides and the volatilization of fluorides are accelerated, particularly, the complete decomposition of toxic substances, namely aluminum nitride and cyanides is promoted, the high-temperature reaction process of the whole electric arc furnace smelting is strengthened, and the production efficiency is improved.
Drawings
FIG. 1 is a process flow diagram of the method for preparing the AlSiFe alloy by plasma jet feeding with the aluminum ash 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 phase composition of a treated secondary aluminum ash, and the phase composition and content of the aluminum ash produced by different enterprises are different due to different casting and refining processes.
TABLE 1 phase composition of treated Secondary aluminum Ash
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
Table 3 shows the main components of a low-alumina fly ash.
TABLE 3 Main Components of Low-aluminum fly ash
Table 4 shows the main components of a diatomaceous earth residue.
TABLE 4 main components of diatomaceous earth waste residue
Example 1
The plasma jet feeding process of preparing Al-Si-Fe alloy with aluminum ash as material includes the following steps:
step 1, respectively preparing aluminum ash, waste cathode carbon blocks in overhaul residues of an aluminum electrolytic cell, fly ash and diatomite waste residues into powder with the granularity of less than 100 meshes;
step 2, calculating the mass of secondary aluminum ash, waste cathode carbon blocks, fly ash and diatomite waste residues required for reducing metal oxides by taking fixed carbon contained in the waste cathode carbon blocks as a reducing agent according to a stoichiometric ratio according to the components of the target aluminum-silicon-iron alloy, wherein the mass of the secondary aluminum ash, the waste cathode carbon blocks, the fly ash and the diatomite waste residues is calculated, the metal aluminum in the secondary aluminum ash is calculated according to the condition that all the metal aluminum enters the aluminum-silicon-iron alloy, the aluminum nitride is completely decomposed into metal aluminum and nitrogen, the obtained metal aluminum is also calculated according to the condition that all the metal aluminum enters the aluminum-silicon-iron alloy, and finally the mass ratio of the obtained aluminum ash, the fly ash, the diatomite waste residues to the waste cathode carbon blocks is 1:10:1: 6; putting the secondary aluminum ash, the waste cathode carbon block, the fly ash and the diatomite waste residue powder into a mixer together for uniformly mixing;
step 3, starting the electric arc furnace and gradually increasing the temperature in the furnace, wherein the electrode adopted by the electric arc furnace is a hollow electrode, and a hollow channel in the middle of the electrode is connected with a flame outflow port of the plasma generator; the diameter of the hollow channel in the middle of the electrode is 200 mm. When the temperature of the bottom arc zone is 2300 ℃, the generated plasma flame flow is taken as a carrier to send the powdery material to the arc reaction zone through the hollow channel, the temperature of the plasma flame flow is 300 ℃, and the working gas of the plasma generator is air; when the smelting process reaches 3 hours, discharging the formed ferro-silicon-aluminum alloy melt from the bottom of the electric arc furnace and carrying out external refining, wherein the used refining agent contains sodium chloride, potassium chloride and cryolite, and the proportion ranges of the components are 50% of sodium chloride, 40% of potassium chloride and 10% of cryolite; refining at 900 ℃ 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;
step 4, leaching the soot collected from the top of the electric arc furnace by water, 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 sodium carbonate and sodium chloride are recovered from the leachate 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 plasma jet feeding process of preparing Al-Si-Fe alloy with aluminum ash as material includes the following steps:
step 1, respectively preparing aluminum ash, waste cathode carbon blocks in overhaul residues of an aluminum electrolytic cell, fly ash and diatomite waste residues into powder with the granularity of less than 100 meshes;
step 2, according to the components of the target ferro-silicon-aluminum alloy: 35 percent of aluminum, 54 percent of silicon and the balance of iron, calcium, titanium and other trace metals; calculating the mass of secondary aluminum ash, waste cathode carbon blocks, coal ash and diatomite waste residues required for reducing metal oxides by taking fixed carbon contained in the waste cathode carbon blocks as a reducing agent according to a stoichiometric ratio, wherein the mass of metal aluminum in the secondary aluminum ash is calculated according to the condition that all the metal aluminum enters an aluminum-silicon-iron alloy, all the aluminum nitride is decomposed into metal aluminum and nitrogen, the obtained metal aluminum is calculated according to the condition that all the metal aluminum enters the aluminum-silicon-iron alloy, and the mass ratio of the obtained aluminum ash, the coal ash, the diatomite waste residues to the waste cathode carbon blocks is 2:8:1: 6; putting the secondary aluminum ash, the waste cathode carbon block, the fly ash and the diatomite waste residue powder into a mixer together for uniformly mixing;
step 3, starting the electric arc furnace and gradually increasing the temperature in the furnace, wherein the electrode adopted by the electric arc furnace is a hollow electrode, and a hollow channel in the middle of the electrode is connected with a flame outflow port of the plasma generator; the diameter of the hollow channel in the middle of the electrode is 100 mm. When the temperature of the bottom arc zone is 2100 ℃, the generated plasma flame flow is used as a carrier to send the powdery material to the arc reaction zone through the hollow channel, the temperature of the plasma flame flow is 1700 ℃, the working gas of the plasma generator is carbon monoxide, 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, and the used refining agent contains sodium chloride, potassium chloride and cryolite, wherein the proportion range of each component is 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 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, 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 and sodium chloride are recovered from the leachate through evaporation, leaching slag is dried and then subjected to high-temperature melting, 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 the 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 the ferro-aluminium and silicon by the electric arc furnace.
Example 3
The plasma jet feeding process of preparing Al-Si-Fe alloy with aluminum ash as material includes the following steps:
step 1, respectively preparing aluminum ash, waste cathode carbon blocks in overhaul residues of an aluminum electrolytic cell, fly ash and diatomite waste residues into powder with the granularity of less than 100 meshes;
step 2, according to the components of the target ferro-silicon-aluminum alloy: 43 percent of aluminum, 47 percent of silicon and the balance of iron, calcium, titanium and other trace metals; calculating the mass of secondary aluminum ash, waste cathode carbon blocks, coal ash and diatomite waste residues required for reducing metal oxides by taking fixed carbon contained in the waste cathode carbon blocks as a reducing agent according to a stoichiometric ratio, wherein the mass of metal aluminum in the secondary aluminum ash is calculated according to the condition that all the metal aluminum enters an aluminum-silicon-iron alloy, all the aluminum nitride is decomposed into metal aluminum and nitrogen, the obtained metal aluminum is calculated according to the condition that all the metal aluminum enters the aluminum-silicon-iron alloy, and the mass ratio of the obtained aluminum ash, the coal ash, the diatomite waste residues to the waste cathode carbon blocks is 2:2:2: 3; putting the secondary aluminum ash, the waste cathode carbon block, the fly ash and the diatomite waste residue powder into a mixer together for uniformly mixing;
step 3, starting the electric arc furnace and gradually increasing the temperature in the furnace, wherein the electrode adopted by the electric arc furnace is a hollow electrode, and a hollow channel in the middle of the electrode is connected with a flame outflow port of the plasma generator; the diameter of the hollow channel in the middle of the electrode is 20 mm. When the temperature of the bottom arc zone is 1900 ℃, the generated plasma flame flow is taken as a carrier to send the powdery material to the arc reaction zone through the hollow channel, the temperature of the plasma flame flow is 3000 ℃, and the working gas of the plasma generator is argon; when the smelting process reaches 1 hour, discharging the formed ferro-silicon-aluminum alloy melt from the bottom of the electric arc furnace and carrying out external refining, wherein the used 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; refining at 1500 ℃ 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 20 ℃, the liquid-solid ratio in the leaching process is 2:1, the leaching time is 3 hours, filtering is performed after leaching, sodium carbonate and sodium chloride are recovered from the leaching solution through evaporation, leaching slag is dried and then subjected to high-temperature melting, the melting temperature is 1000 ℃, so that fluoride is separated from oxide, the recovered fluoride electrolyte is returned to an electrolytic cell for use, and the 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 the ferro-aluminium-silicon by the electric arc furnace.

Claims (10)

1. The method for preparing the ferro-silicon-aluminum alloy by using the aluminum ash as the raw material through plasma jet feeding is characterized by comprising the following steps of:
step 1, respectively preparing secondary aluminum ash, waste cathode carbon blocks in overhaul residues of an aluminum electrolytic cell, fly ash and diatomite waste residues into powder;
step 2, determining the use amounts of secondary aluminum ash, waste cathode carbon blocks, fly ash and diatomite waste residues according to the components of the target ferro-silicon-aluminum alloy, and reducing Al in the secondary aluminum ash by using fixed carbon contained in the waste cathode carbon blocks as a reducing agent according to a stoichiometric ratio2O3、SiO2The amount of metal aluminum and silicon generated by oxides is calculated, and then the Al of the waste residue of fly ash and diatomite reduced by the waste cathode carbon block is calculated2O3、SiO2The amount of the metal aluminum and silicon obtained by the oxide is adjusted by the amount of the metal aluminum and silicon obtained by reducing the fly ash and the diatomite waste residue, so that the components of the aluminum and the silicon in the prepared aluminum-silicon-iron alloy and the amounts of the secondary aluminum ash, the fly ash, the diatomite waste residue and the waste cathode carbon block are obtained; putting the secondary aluminum ash, the waste cathode carbon block, the fly ash and the diatomite waste residue powder into a mixer together for uniformly mixing;
step 3, starting the electric arc furnace and gradually increasing the temperature in the furnace, wherein the electrode adopted by the electric arc furnace is a hollow electrode, and a hollow channel in the middle of the electrode is connected with a flame outflow port of the plasma generator; when the temperature of the bottom arc zone is 1900-; 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 by water and 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 and sodium chloride are recovered from the leachate through evaporation, the leached slag is dried and then melted at high temperature, the melting temperature is higher than 1000 ℃, so that fluoride is separated from oxide, the recovered fluoride electrolyte is returned to an electrolytic cell for use, and the 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 for preparing the sendust by plasma jet feeding with the aluminum ash as the raw material according to claim 1, wherein the secondary aluminum ash comprises the following components by mass: al (Al)2O340~80%,AlN≤20%,Al≤10%,SiO2≤5%,Na2O≤5%,Fe2O3Less than or equal to 5 percent, less than or equal to 10 percent of chloride and less than or equal to 10 percent of fluoride.
3. The method for preparing the sendust by plasma jet feeding with the aluminum ash as the raw material according to claim 1, wherein the waste cathode carbon block comprises the following components by mass: 60-80% of C and Al2O3Less than or equal to 3 percent, Na 4-10 percent and fluoride electrolyte 10-20 percent.
4. The method for preparing the sendust by plasma jet feeding with the aluminum ash as the raw material according to claim 1, wherein the fly ash comprises the following components 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 by plasma jet feeding with the aluminum ash as the raw material according to claim 1, wherein the waste diatomite slag comprises the following components in percentage by mass: al (Al)2O3≤5%,SiO280~99%,Fe2O3≤10%。
6. The method for preparing the sendust by plasma jet feeding with the aluminum ash as the raw material according to claim 1, wherein in step 1, the particle sizes of the secondary aluminum ash, the waste cathode carbon block, the fly ash and the diatomite waste residue powder are all less than 100 meshes.
7. The method for preparing AlSiFe alloy by plasma jet feeding with aluminum ash as raw material as claimed in claim 1, wherein in step 3, the diameter of the hollow channel in the middle of the electrode is 20mm-200 mm.
8. The method for preparing AlSiFe alloy by plasma jet feeding with aluminum ash as raw material as claimed in claim 1, wherein in step 3, the flow rate and flow velocity of the plasma flame flow are controllable, and the temperature of the plasma flame flow is between 300 ℃ and 3000 ℃.
9. The method for preparing AlSiFe alloy by plasma jet feeding with aluminum ash as raw material as claimed in claim 1, wherein in step 3, the working gas of the plasma generator is one of argon, air and carbon monoxide.
10. The method for preparing the sendust by plasma jet feeding with the aluminum ash as the raw material according to claim 1, wherein in step 3, the refining agent used for the external refining contains sodium chloride, potassium chloride and cryolite, the proportion of each component is 30-60% of sodium chloride, 30% or less of potassium chloride and 30% or less of cryolite; the refining temperature is 900-1500 ℃.
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