CN110016565A - The method for producing AL-Si-Fe alloy as raw material coreless armature feeding using waste refractory materials - Google Patents

The method for producing AL-Si-Fe alloy as raw material coreless armature feeding using waste refractory materials Download PDF

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CN110016565A
CN110016565A CN201910404104.1A CN201910404104A CN110016565A CN 110016565 A CN110016565 A CN 110016565A CN 201910404104 A CN201910404104 A CN 201910404104A CN 110016565 A CN110016565 A CN 110016565A
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waste
refractory materials
alloy
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waste refractory
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CN110016565B (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

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  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
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  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Processing Of Solid Wastes (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The present invention provides a kind of method for producing AL-Si-Fe alloy as raw material coreless armature feeding using waste refractory materials, using waste refractory materials as raw material, using waste cathode of aluminum electrolytic cell carbon block as reducing agent, the aluminium content in raw material is adjusted by additive of flyash, adjusts the silicone content in raw material by additive of diatomite waste residue, material of the high temperature reduction based on aluminium oxide and silica and then prepares certain ingredients AL-Si-Fe alloy in electric arc furnaces；Using coreless armature conveying powder material, entire arc furnace smelting procedure can be strengthened, promote the reduction of oxide and the volatilization of fluoride, especially accelerate the decomposition of noxious material cyanide, and in material fluoride, chloride and alkali metal volatilization and recycling, production efficiency is improved, production cost is reduced, the comprehensive utilization of a variety of dangerous wastes, solid waste is realized in the same technique.

Description

The method for producing AL-Si-Fe alloy as raw material coreless armature feeding using waste refractory materials
Technical field
The present invention relates to electrometallurgy fields, more particularly to one kind to produce aluminium by raw material coreless armature feeding of waste refractory materials The method of Antaciron.
Background technique
Ferro-silicon-aluminium production method is broadly divided into metal mix-melting method and electric reduction process.Metal mix-melting method is to utilize pure metal Aluminium, silicon, iron form alloy to mixing in the molten state according to a certain percentage；Electric reduction process is containing aluminium, silicon, iron Oxide is raw material, using carbonaceous material as reducing agent, prepares alloy by electric arc furnaces reduction melting.Wherein metal mix-melting method exists The problems such as the reheating of pure metal, secondary scaling loss and high production cost.And there is also pure raw mineral materials is short for electric reduction process It lacks, the problems such as production process is less economical.
Aluminium cell is the capital equipment for producing metallic aluminium.Aluminium cell can generate a large amount of electrolysis after damaged overhaul Groove overhaul slag.Slag from delining is made of cathode carbon pieces, cathode paste, refractory brick, insulating brick, Impervious Materials and heat-insulating shield etc..Further may be used Slag from delining is divided into the waste refractory materials liner (Impervious Materials, refractory brick, insulating brick) and waste cathode carbon corroded by villiaumite electrolyte Two major parts of block (cathode carbon pieces, cathode paste), and the mass ratio of waste cathode carbon block and waste refractory materials about respectively accounts for 50%. Currently, every one ton of metallic aluminium of production generates the waste cathode carbon block of 5-10kg and the waste refractory materials of 5-10kg.
Waste refractory materials are mainly situated in the useless dry type impervious material of cathode carbon pieces lower part, account for about the 90% of waste refractory materials. The main component of dry type impervious material raw material is aluminium oxide and silica, the useless Impervious Materials main component after being corroded by electrolyte osmosis It is nepheline (NaAlSiO4) or albite (NaAlSi3O8), additionally the electrolysis of fluorides matter containing 10-15%, iron oxide, oxygen Change other oxides and the metals such as carbide impurity and a small amount of aluminium, silicon, ferro-silicon-aluminium and alloy such as calcium, aluminium carbide.Since these are useless There is also more fluorides in refractory material, therefore also by for dangerous waste.Currently, the useless fire proofed wood generated when aluminium cell overhaul Effective recycling and processing is not yet received in material, generally based on landfill disposal.Due to containing many electrolysis in waste refractory materials The soluble substances such as oxide of matter fluoride, sodium, long-term stack can generate significant damage to underground water and ambient enviroment.
The main component of waste cathode carbon block is carbonaceous material, other than carbonaceous material, component it is most be exactly electrolyte.It is useless Electrolyte component mainly has NaF, Na in cathode carbon pieces3AlF6、Na5Al3F14And CaF2Deng.Charcoal contains in aluminium electroloysis waste cathode carbon block Amount is generally in 60%-70%, electrolyte components content 15-25%.In addition, aluminium electroloysis is given up, there are the alkali of 4%-8% gold in cathode Belong to, mainly metallic sodium.When there is sylvite in electrolyte ingredient, there is also metallic potassiums in waste cathode carbon block.Except above-mentioned three kinds of masters It wants outside ingredient, a small amount of carbide, nitride, oxide and cyanide is also contained in waste cathode carbon block, wherein cyanide content Account for about the 0.1%-0.2% of waste cathode carbon gross mass.NaCN, complicated cyanide and fluoride in waste cathode carbon block are to endanger ring The principal element in border.Cyanide and most of fluoride are all dissolved in water, and the waste and old cathode carbon block accumulated for a long time can pollute Underground water and surface water cause seriously to pollute to environment.Two classes, Yi Leishi are divided into for the processing of waste cathode of aluminum electrolytic cell carbon block Processing technique, even if waste cathode carbon block of material is utilized by innoxious rear landfill or by other industry, such as pyrohydrolysis technology, combustion Burn generation technology, make high-speed rail industry slag former, the fuel as cement industry and raw mineral materials, be converted into can fill it is lazy Property material etc.；Another kind of is recovery and utilization technology, mainly the fluoride and charcoal in recycling waste cathode carbon block, as wet-leaching returns Receive fluoride, as cathode, anode carbon block additive, floatation separates electrolysis of fluorides matter and carbon block etc., but existing useless cathode Industrialized level has not yet been reached in the processing of carbon block.
One ton of coal of every burning can generate 0.15-0.3 tons of flyash, and the high coal of ash content can at most generate 0.4-0.5 tons of powder Coal ash.Currently, the fine coal ash quantity that China generates every year reaches 600,000,000 tons or more.A small amount of aluminous fly-ash can be used for extracting oxidation Aluminium, and a large amount of low aluminium powder coal ash is then mainly for the production of various construction materials, such as cement blending agent, concrete additive and builds Material deep processed product, and floating bead is extracted to produce fire resisting and thermal insulation material from flyash, but these methods can not be from root The Utilizing question of flyash is solved in sheet.Also, it is low to produce construction material added value, must be abutted using enterprise populous Big city, therefore this using method mainly east China province use.And it is distributed in Shanxi, Inner Mongol, Ningxia, Shaanxi, sweet The flyash on the ground such as respectful and Xinjiang is not utilized effectively, most of still to be handled in a manner of storing up, filling.
The roll of aluminium processing enterprise needs to be cooled down and lubricated using ROLLING OIL in process of production, and ROLLING OIL is using It just needs to filter after a period of time, and filter medium is using diatomite material.During aluminium rolling, due to aluminium compared with Soft, the abrasion of roll is less, so abrasion powder of the impurity in ROLLING OIL mainly from aluminium.When diatomite uses a timing Between after filtering accuracy when the use standard of ROLLING OIL is not achieved, it is necessary to regularly replace.The oil-containing waste diatomite quilt replaced It is considered as dangerous waste, not only there is the risk of environmental pollution, while also results in the significant wastage of resource.The main component of China's diatomite For silica, aluminium oxide and iron oxide.Diatomite waste residue caused by the ROLLING OIL of aluminum fabrication plant filtering at present, which mainly contains, to be rolled Liquefaction and aluminium powder, wherein ROLLING OIL can carry out de-oiling with oil removal machine, and the grease of abjection can be used for producing kerosene, and diatomite waste residue It is still not given to effectively handle.
As can be seen from the above analysis: dangerous waste, the solid waste that existing electrolytic aluminium, aluminium processing and power industry generate all are to be divided Other places reason, it is largely in the harmless treatment stage, effective resource utilization is still in conceptual phase, causes not from root The problem of environmental pollution of these solid waste is solved in sheet.
Summary of the invention
The present invention provides a kind of method for producing AL-Si-Fe alloy as raw material coreless armature feeding using waste refractory materials, with Waste refractory materials are raw material, using waste cathode of aluminum electrolytic cell carbon block as reducing agent, are adjusted in raw material using flyash as additive Aluminium content, silicone content, material of the high temperature reduction based on aluminium oxide and silica and then preparation certain ingredients aluminium in electric arc furnaces Antaciron；During high temperature reduction realize waste cathode carbon block in cyanide decomposition and material in fluoride and alkali gold The volatilization and recycling of category, realize the comprehensive utilization of a variety of dangerous wastes, solid waste in the same technique.In order to achieve the above object, originally Invention uses following technical scheme:
In the method that waste refractory materials produce AL-Si-Fe alloy as raw material coreless armature feeding, include the following steps:
Step 1, powder is respectively prepared with waste cathode carbon block, flyash in the waste refractory materials in aluminium cell slag from delining；
Step 2, the use of waste refractory materials, flyash and waste cathode carbon block is determined according to the ingredient of target AL-Si-Fe alloy Amount stoichiometrically calculates Al in reduction waste refractory materials using fixed carbon contained in waste cathode carbon block as reducing agent2O3、SiO2 The amount of metallic aluminium, silicon that oxide generates, then calculate with Al in waste cathode carbon block reduction flyash2O3、SiO2Obtained by oxide Metallic aluminium, silicon amount, metallic aluminium, the silicon that the aluminium obtained with reduction flyash, silicon amount allotment reduction waste refractory materials obtain The ingredient and waste refractory materials, flyash and waste cathode carbon block of aluminium in prepared AL-Si-Fe alloy, silicon can be obtained in amount Dosage；Waste refractory materials, flyash and waste cathode carbon block powder are put into togerther in blender and are uniformly mixed；
Step 3, start electric arc furnaces, and in-furnace temperature be gradually increased, the electrode that the electric arc furnaces uses for coreless armature, Hollow passageway among electrode is connected with the compressed gas pipeline of conveying powder material, when bottom arc area temperature is 1700-2100 DEG C when, granular material is sent to electric arc reaction area through hollow passageway using compressed gas as carrier, after fusion process reaches 2-6h The AL-Si-Fe alloy melt to be formed is released from electric arc furnace bottom and carries out external refining, AL-Si-Fe alloy can be obtained, the alloy It can be used as deoxidizer in steel production and magnesium smelting reducing agent, refining slag returns to burden process and continues to use；
Step 4, by from electric arc furnaces collected overhead to cigarette ash water logging and filter, extraction temperature is 20~100 DEG C, leaching Process liquid-solid ratio is 2~10:1 out, and extraction time is 0.5~3h, is filtered after leaching, and leachate recycles sodium carbonate by evaporation, Leached mud carries out high temperature melting after the drying, and fusion temperature is not less than 1000 DEG C, so that fluoride is separated with oxide, recycling Electrolysis of fluorides matter returns to electrolytic cell and uses, and slag phase oxide returns to electric arc furnaces feed proportioning workshop as electric arc furnace smelting aluminium silicon The raw material of iron.
The ingredient of above-mentioned waste refractory materials is in mass ratio are as follows: Na2O 5~30%, Al2O315~50%, SiO210~ 50%, Fe2O3≤ 10%, K2O≤3%, CaO≤3%, F≤10%.
The ingredient of above-mentioned waste cathode carbon block is in mass ratio are as follows: C 60~80%, Al2O30~3%, Na 4~10%, fluorination Object electrolyte 10~20%, electrolysis of fluorides matter are mainly ice crystal, sodium fluoride and calcirm-fluoride, it is also possible to contain lithium fluoride and fluorine Change potassium.
Above-mentioned fine coal ash composition is in mass ratio are as follows: Al2O315~50%, SiO230~50%, Fe2O30~10%, CaO≤5%, MgO≤5%, Na2O≤3%, K2O≤3%, TiO2≤ 3%, other single metal oxide contents are less than 1%.
The ingredient of above-mentioned paper pulp dry powder is in mass ratio are as follows: calcium lignosulfonate >=90%, butt moisture >=8%.
Above-mentioned steps 1, the waste refractory materials, waste cathode carbon block, flyash and diatomite waste residue powder granularity are small In 100 mesh.
Above-mentioned steps 3, the diameter in the electrode central hollow channel are 20mm-200mm.
Above-mentioned steps 3, the compressed gas are one of argon gas, air, carbon monoxide.
The pressure of above-mentioned steps 3, the compressed gas controls between 0.1-0.8MPa.
Above-mentioned steps 3, refining agent used in external refining contain sodium chloride, potassium chloride and ice crystal, each component ratio range Sodium chloride 30~60%, potassium chloride≤30%, ice crystal≤30%；900~1500 DEG C of refining temperature.
Compared with prior art, the beneficial effects of the present invention are:
1, present waste refractory materials, waste cathode carbon block and flyash are to separate processing, that is to say, that are used more Kind technique and more set processing systems.Wherein, the processing of waste refractory materials is usually to fill or store up again after carrying out harmless treatment. Waste cathode carbon block treatment process is divided into wet process and pyrogenic process, and based on wet process, is to be leached using strong acid or highly basic, makes fluorine Compound is converted into soluble hydrogen fluoride or sodium fluoride is separated with carbonaceous material, and treatment process equally generates a large amount of containing acid or containing alkali Waste water be easy to cause secondary pollution.The present invention be directed to a variety of dangerous wastes, solid waste and a kind of integrated treatment technology developed, and give up Refractory material, waste cathode carbon block and flyash all complete processing and recycling in an electrocarbothermic reduction process.In carbon thermal reduction The pyrolytic of main noxious material cyanide is not only realized in the process, but also realizes waste refractory materials and waste cathode carbon block The vaporization at high temperature of middle fluoride separates, the metal oxide in treatment process in waste refractory materials and waste cathode carbon block be reduced into Enter AL-Si-Fe alloy, generation of the whole process without waste residue and waste water is a kind of environmentally protective treatment process.
2, the prior art when handling waste refractory materials, the dangerous wastes such as waste cathode carbon block mainly based on innoxious, minimizing, Treatment process of the invention realizes the resource utilization of waste, i.e., with waste cathode carbon block while innoxious, minimizing In fixed carbon as reducing agent by aluminium oxide, silica, the iron oxide etc. in waste refractory materials, diatomite waste residue and flyash It restores in a metallic form, while fluoride and alkali metal is also recycled, realize the treatment of wastes with processes of wastes against one another, and whole A technical process is closed cycle.
3, using secondary waste refractory materials as raw material, aluminium content in raw material, silicone content are adjusted as additive using flyash, A variety of wastes are not only utilized in this batching mode, and are easy to prepare the AL-Si-Fe alloy of various composition, and then adapt to electricity The smelting process of arc furnace makes smelting process and alloying component be easy to regulate and control, and has advantageously reduced production cost, is also subsequent processing It creates condition.
4, using coreless armature conveying powder material, entire arc furnace smelting procedure can be strengthened, promote going back for oxide Former and fluoride volatilization, especially accelerates the decomposition of noxious material cyanide, improves production efficiency, reduces production cost.
Detailed description of the invention
Fig. 1 is the technique stream for the method that the present invention produces AL-Si-Fe alloy using waste refractory materials as raw material coreless armature feeding Cheng Tu.
Specific embodiment
For following waste material, technical solution of the present invention is elaborated.
Table 1 is a kind of main component of waste refractory materials.Due to electrolysis process and electrolyte ingredient and bath life Difference, there are difference for the ingredient and content of the waste refractory materials of different enterprises.
A kind of main component of the waste refractory materials of table 1
Table 2 is a kind of main component of waste cathode carbon block, due to electrolysis process and electrolyte ingredient and bath life Difference, there are difference for the ingredient and content of the waste cathode carbon block of different enterprises.
A kind of main component of the waste cathode carbon block of table 2
Table 3 is a kind of main component of low aluminium powder coal ash.
A kind of main component of low aluminium powder coal ash of table 3
Embodiment 1
In the method that waste refractory materials produce AL-Si-Fe alloy as raw material coreless armature feeding, include the following steps:
Step 1, powder is respectively prepared with waste cathode carbon block, flyash in the waste refractory materials in aluminium cell slag from delining, Granularity is 100 mesh；
Step 2, according to the ingredient of target AL-Si-Fe alloy: aluminum content 25%, silicon content 65%, remaining for iron, calcium, titanium and Other trace meters stoichiometrically calculate reducing metal oxide institute as reducing agent using fixed carbon contained in waste cathode carbon block The quality of the waste refractory materials, waste cathode carbon block, flyash that need, finally obtains waste refractory materials, flyash and waste cathode carbon block Mass ratio be 1:6:4, by waste refractory materials, waste cathode carbon block, flyash be put into togerther in blender be uniformly mixed；
Step 3, start electric arc furnaces, and in-furnace temperature be gradually increased, the electrode that the electric arc furnaces uses for coreless armature, Hollow passageway among electrode is connected with the compressed gas pipeline of conveying powder material, when bottom arc area temperature is 2100 DEG C, Granular material is sent to electric arc reaction area through hollow passageway using compressed air as carrier, from electric arc furnaces after fusion process reaches 6h Bottom releases the AL-Si-Fe alloy melt to be formed and carries out external refining；The diameter of the hollow passageway is 200mm, pressure control In 0.1MPa, refining agent used contains sodium chloride, potassium chloride and ice crystal, and each component ratio range is sodium chloride 50%, chlorination Potassium 40%, ice crystal 10%；1500 DEG C of refining temperature, AL-Si-Fe alloy can be obtained, the alloy can be used as deoxidizer in steel production and Magnesium smelting reducing agent, refining slag return to burden process and continue to use；
Step 4, by from electric arc furnaces collected overhead to cigarette ash water logging and filter, extraction temperature is 95 DEG C, is leached Journey liquid-solid ratio is 10:1, and extraction time 0.5h is filtered after leaching, and leachate passes through evaporation recycling sodium carbonate；Leached mud is drying High temperature melting is carried out after dry, fusion temperature is 1200 DEG C, so that fluoride is separated with oxide, the electrolysis of fluorides matter of recycling is returned It returns electrolytic cell to use, slag phase oxide returns to raw material of the electric arc furnaces feed proportioning workshop as electric arc furnace smelting ferro-silicon-aluminium.
Embodiment 2
In the method that waste refractory materials produce AL-Si-Fe alloy as raw material coreless armature feeding, include the following steps:
Step 1, powder is respectively prepared with waste cathode carbon block, flyash in the waste refractory materials in aluminium cell slag from delining, Granularity is 100 mesh；
Step 2, according to the ingredient of target AL-Si-Fe alloy: aluminum content 27%, silicon content 63%, remaining for iron, calcium, titanium and Other trace meters；Reducing metal oxide institute is stoichiometrically calculated as reducing agent using fixed carbon contained in waste cathode carbon block The quality of the waste refractory materials, flyash, waste cathode carbon block that need, obtains the matter of waste refractory materials, flyash and waste cathode carbon block Amount is than being 1:3:2；Waste refractory materials, waste cathode carbon block, flyash are put into togerther in blender and are uniformly mixed；
Step 3, start electric arc furnaces, and in-furnace temperature be gradually increased, the electrode that the electric arc furnaces uses for coreless armature, Hollow passageway among electrode is connected with the compressed gas pipeline of conveying powder material, when bottom arc area temperature is 19000 DEG C, Granular material is sent to electric arc reaction area through hollow passageway using compressed argon as carrier, from electric arc furnaces after fusion process reaches 4h Bottom releases the AL-Si-Fe alloy melt to be formed and carries out external refining；The diameter of the hollow passageway is 100mm, pressure control In 0.4MPa；Refining agent used contains sodium chloride, potassium chloride and ice crystal, and each component ratio range is sodium chloride 40%, chlorination Potassium 40%, ice crystal 20%；1200 DEG C of refining temperature, AL-Si-Fe alloy can be obtained；The alloy can be used as deoxidizer in steel production and Magnesium smelting reducing agent, refining slag return to burden process and continue to use；
Step 4, by from electric arc furnaces collected overhead to cigarette ash water logging and filter, extraction temperature is 60 DEG C, is leached Journey liquid-solid ratio is 6:1, and extraction time 1.5h is filtered after leaching, and leachate is being dried by evaporation recycling sodium carbonate, leached mud After carry out high temperature melting, 1100 DEG C of fusion temperature, so that fluoride is separated with oxide, the electrolysis of fluorides matter of recycling returns to electricity It solves slot to use, slag phase oxide returns to raw material of the electric arc furnaces feed proportioning workshop as electric arc furnace smelting ferro-silicon-aluminium.
Embodiment 3
In the method that waste refractory materials produce AL-Si-Fe alloy as raw material coreless armature feeding, include the following steps:
Step 1, powder is respectively prepared with waste cathode carbon block, flyash in the waste refractory materials in aluminium cell slag from delining, Granularity is 100 mesh；
Step 2, according to the ingredient of target AL-Si-Fe alloy: aluminum content 31%, silicon content 58%, remaining for iron, calcium, titanium and Other trace meters；Reducing metal oxide institute is stoichiometrically calculated as reducing agent using fixed carbon contained in waste cathode carbon block The quality of the waste refractory materials, flyash, waste cathode carbon block that need, obtains the matter of waste refractory materials, flyash and waste cathode carbon block Amount is than being 1:1:1；Waste refractory materials, waste cathode carbon block, flyash are put into togerther in blender and are uniformly mixed；
Step 3, start electric arc furnaces, and in-furnace temperature be gradually increased, the electrode that the electric arc furnaces uses for coreless armature, Hollow passageway among electrode is connected with the compressed gas pipeline of conveying powder material, when bottom arc area temperature is 1700 DEG C, Granular material is sent to electric arc reaction area through hollow passageway as carrier to compress CO gas, after fusion process reaches 2h The AL-Si-Fe alloy melt to be formed is released from electric arc furnace bottom and carries out external refining；The diameter of the hollow passageway is 20mm, Pressure is controlled in 0.8MPa；Refining agent used contains sodium chloride, potassium chloride and ice crystal, and each component ratio range is sodium chloride 60%, potassium chloride 10%, ice crystal 30%；900 DEG C of refining temperature, AL-Si-Fe alloy can be obtained, which can be used as making steel Deoxidier and magnesium smelting reducing agent, refining slag return to burden process and continue to use；
Step 4, by from electric arc furnaces collected overhead to cigarette ash water logging and filter, extraction temperature is 20 DEG C, is leached Journey liquid-solid ratio is 2:1, and extraction time 3h is filtered after leaching, and leachate is by evaporation recycling sodium carbonate, and leached mud is after the drying High temperature melting is carried out, 1000 DEG C of fusion temperature, so that fluoride is separated with oxide, the electrolysis of fluorides matter of recycling returns to electrolysis Slot uses, and slag phase oxide returns to raw material of the electric arc furnaces feed proportioning workshop as electric arc furnace smelting ferro-silicon-aluminium.

Claims (10)

1. the method for producing AL-Si-Fe alloy as raw material coreless armature feeding using waste refractory materials, which is characterized in that including as follows Step:
Step 1, powder is respectively prepared with waste cathode carbon block, flyash in the waste refractory materials in aluminium cell slag from delining；
Step 2, the dosage of waste refractory materials, flyash and waste cathode carbon block is determined according to the ingredient of target AL-Si-Fe alloy, with Contained fixed carbon is that reducing agent stoichiometrically calculates Al in reduction waste refractory materials in waste cathode carbon block2O3、SiO2Oxide The amount of the metallic aluminium of generation, silicon, then calculate with Al in waste cathode carbon block reduction flyash2O3、SiO2The obtained metal of oxide The amount of aluminium, silicon, the amount of the aluminium obtained with reduction flyash, the metallic aluminium that silicon amount allotment reduction waste refractory materials obtain, silicon Obtain aluminium, the ingredient of silicon and the dosage of waste refractory materials, flyash and waste cathode carbon block in prepared AL-Si-Fe alloy； Waste refractory materials, flyash and waste cathode carbon block powder are put into togerther in blender and are uniformly mixed；
Step 3, start electric arc furnaces, and in-furnace temperature is gradually increased, the electrode that the electric arc furnaces uses is coreless armature, electrode Intermediate hollow passageway is connected with the compressed gas pipeline of conveying powder material, when bottom arc area temperature is 1700-2100 DEG C, Granular material is sent to electric arc reaction area through hollow passageway using compressed gas as carrier, from electric arc after fusion process reaches 2-6h Furnace bottom releases the AL-Si-Fe alloy melt to be formed and carries out external refining, AL-Si-Fe alloy can be obtained, which can be used as Deoxidizer in steel production and magnesium smelting reducing agent, refining slag return to burden process and continue to use；
Step 4, by from electric arc furnaces collected overhead to cigarette ash water logging and filter, extraction temperature is 20~100 DEG C, is leached Journey liquid-solid ratio is 2~10:1, and extraction time is 0.5~3h, is filtered after leaching, and leachate is leached by evaporation recycling sodium carbonate Slag carries out high temperature melting after the drying, and fusion temperature is not less than 1000 DEG C, so that fluoride is separated with oxide, the fluorination of recycling Object electrolyte returns to electrolytic cell and uses, and slag phase oxide returns to electric arc furnaces feed proportioning workshop as electric arc furnace smelting ferro-silicon-aluminium Raw material.
2. the method according to claim 1 for producing AL-Si-Fe alloy as raw material coreless armature feeding using waste refractory materials, It is characterized in that, the ingredient of waste refractory materials is in mass ratio are as follows: Na2O 5~30%, Al2O315~50%, SiO210~ 50%, Fe2O3≤ 10%, K2O≤3%, CaO≤3%, F≤10%.
3. the method according to claim 1 for producing AL-Si-Fe alloy as raw material coreless armature feeding using waste refractory materials, It is characterized in that, the ingredient of waste cathode carbon block is in mass ratio are as follows: C 60~80%, Al2O30~3%, Na 4~10%, fluorination Object electrolyte 10~20%.
4. the method according to claim 1 for producing AL-Si-Fe alloy as raw material coreless armature feeding using waste refractory materials, It is characterized in that, fine coal ash composition is in mass ratio are as follows: Al2O315~50%, SiO230~50%, Fe2O3≤ 10%, CaO ≤ 5%, MgO≤5%, Na2O≤3%, K2O≤3%, TiO2≤ 3%, other single metal oxide contents are less than 1%.
5. the method according to claim 1 for producing AL-Si-Fe alloy as raw material coreless armature feeding using waste refractory materials, It is characterized in that, the ingredient of diatomite waste residue is in mass ratio are as follows: calcium lignosulfonate >=90%, butt moisture >=8%.
6. the method according to claim 1 for producing AL-Si-Fe alloy as raw material coreless armature feeding using waste refractory materials, It is characterized in that, step 1, the waste refractory materials, waste cathode carbon block, flyash and diatomite waste residue powder granularity are respectively less than 100 mesh.
7. the method according to claim 1 for producing AL-Si-Fe alloy as raw material coreless armature feeding using waste refractory materials, It is characterized in that, step 3, the diameter in the electrode central hollow channel is 20mm-200mm.
8. the method according to claim 1 for producing AL-Si-Fe alloy as raw material coreless armature feeding using waste refractory materials, It is characterized in that, step 3, the compressed gas is one of argon gas, air, carbon monoxide.
9. the method according to claim 1 for producing AL-Si-Fe alloy as raw material coreless armature feeding using waste refractory materials, It is characterized in that, step 3, the pressure of the compressed gas is controlled between 0.1-0.8MPa.
10. the method according to claim 1 for producing AL-Si-Fe alloy as raw material coreless armature feeding using waste refractory materials, It is characterized in that, step 3, refining agent used in external refining contains sodium chloride, potassium chloride and ice crystal, each component ratio range chlorine Change sodium 30~60%, potassium chloride≤30%, ice crystal≤30%；900~1500 DEG C of refining temperature.
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