CN112899729A - Method for electrolyzing lining waste - Google Patents

Method for electrolyzing lining waste Download PDF

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CN112899729A
CN112899729A CN202110105896.XA CN202110105896A CN112899729A CN 112899729 A CN112899729 A CN 112899729A CN 202110105896 A CN202110105896 A CN 202110105896A CN 112899729 A CN112899729 A CN 112899729A
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waste
lining
alumina
components
content
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覃海棠
李贺松
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/005—Preliminary treatment of scrap
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • C25C3/18—Electrolytes
    • 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 discloses a method for electrolytically treating lining waste, and belongs to the technical field of lining waste treatment. A method of electrolytically treating lining waste comprising the steps of: s1: roughly crushing, namely roughly crushing the removed waste lining material by using a jaw crusher; s2: grinding, namely grinding the coarsely broken agglomerates by using a ball mill, wherein the grinding precision is set to be 150 microns; s3: adjusting the content of alumina in the lining waste, calculating according to the content of alumina in the ground lining waste, adding industrial-grade alumina, and mixing to enable the content of alumina in the mixed material to reach 70-90%. The invention realizes the resource utilization of the valuable components in the lining waste, and the harmful components are decomposed into harmless components; not only saves the additional expense and cost expenditure required by waste landfill, but also realizes the recycling of the solid wastes, generates better economic benefit and has great environmental protection benefit to the society.

Description

Method for electrolyzing lining waste
Technical Field
The invention relates to the technical field of lining waste treatment, in particular to a method for electrolytically treating lining waste.
Background
The lining materials of the casting furnace, the holding furnace, the aluminum electrolytic cell, the magnesium electrolytic cell and other equipment are cleaned in the maintenance process after the service life is reached, and become solid waste. Such lining materials generally consist of refractory materials and insulating materials. The raw materials of the refractory material and the heat insulating material mainly comprise metal oxides such as aluminum oxide, silicon oxide, iron oxide and the like, and belong to recyclable resources.
The compositions of typical kiln lining materials are shown in the following table, and the commonly used lining materials are similar to the following compositions, and only the proportions of various elements are different, and the processing mode is different.
Figure BDA0002917394000000011
However, since the lining material is in direct contact with the production material under high temperature conditions during the operation of the kiln, the lining material is contaminated by the raw materials of the production material and various auxiliary materials and additives used in the production process, such as fluoride, oxide, cyanide and the like contained in the auxiliary materials, additives and slag removal agents, which are harmful to the environment, and solid waste formed by the waste lining of the kiln is caused, which may pollute the environment. If not properly treated, it can cause more serious pollution to the soil and groundwater.
At present, the treatment of the waste lining materials of the furnace kiln in the industry mostly adopts a direct landfill mode or landfill after harmless treatment. Not only the treatment is not thorough, but also a large amount of solid waste is accumulated, and long-term hidden danger exists. Meanwhile, for enterprises, waste treatment needs to pay extra cost and is a great burden.
Therefore, the method has great significance for recycling the waste lining materials of the furnace.
Disclosure of Invention
The invention aims to provide a method for electrolytically treating lining waste, which is used for efficiently treating the lining waste without pollution and recycling resources.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of electrolytically treating lining waste comprising the steps of:
s1: roughly crushing, namely roughly crushing the removed waste lining material by using a jaw crusher;
s2: grinding, namely grinding the coarsely broken agglomerates by using a ball mill, wherein the grinding precision is set to be 150 microns;
s3: adjusting the content of alumina in the lining waste, calculating according to the content of alumina in the ground lining waste, adding industrial-grade alumina, and mixing to enable the content of alumina in the mixed material to reach 70-90%;
s4: preparing an electrolytic cell, wherein the anode and the cathode of the electrolytic cell are made of carbon materials, and the electrolyte is Na3AlF6；
S5: electrolyzing, namely adding the mixture after mixing and proportioning into an electrolytic bath, setting the current intensity to be 100-700 KA, the voltage to be 3.5-3.8V and the electrolyte temperature to be 900-1000 ℃;
s6: obtaining finished products, decomposing harmful components of cyanide into harmless components, reducing metal oxides into metal components, and obtaining aluminum-based alloy products.
Further, before the rough crushing in step S1, the removed lumps with a diameter greater than 500mm in the waste lining material are crushed into small pieces by a crust breaker to meet the inlet requirement of the rough crushing device, and then rough crushing is performed.
Compared with the prior art, the invention provides a method for electrolyzing lining waste, which has the following beneficial effects:
1. according to the invention, the compound components are decomposed into corresponding metals or other components under electrochemical and high-temperature conditions through an electrolytic reaction, so that the resource utilization of valuable components is realized, and harmful components are decomposed into harmless components; compared with the method adopted and treated in the industry, the method can be used for direct landfill or landfill after harmless treatment, so that the extra cost and expense required by waste landfill are saved, the solid waste is recycled, and better economic benefit is generated; the process method has better economic benefit for enterprises and great environmental protection benefit for society.
2. According to the invention, the mixture is ensured by obtaining the mixture with the repose angle less than 39 DEGThe flowability of the electrolyte is convenient for adding the blanking device into the electrolytic bath, and the electrolyte can be better dissolved in the molten electrolyte; the current intensity and the addition amount of the mixture are set according to the required electrolysis speed, so that free control can be realized; so that the Gibbs free energy of the decomposition reaction formula of the harmful ingredients of the cyanide is far less than 0, the reaction is intensively carried out to the right, and the cyanide is decomposed in the aluminum electrolytic cell to generate N2And CO gas and electrolyte components NaF and Al2O3Can enter the electrolyte to realize cyclic utilization, realize harmlessness and reclamation; with Na3AlF6The electrolyte is recycled; the produced aluminum-based alloy keeps liquid state and is deposited below electrolyte liquid, so that the aluminum-based alloy is convenient to collect; and the content of other components in the aluminum-based alloy can be adjusted by adjusting the proportion of the aluminum oxide so as to achieve various required alloy components.
The part which is not involved in the device is the same as the prior art or can be realized by the prior art, the compound components are decomposed into corresponding metals or other components under the conditions of electrochemistry and high temperature through electrolytic reaction, the resource utilization of valuable components is realized, and harmful components are decomposed into harmless components; compared with the method adopted and treated in the industry, the method can be used for direct landfill or landfill after harmless treatment, so that the extra cost and expense required by waste landfill are saved, the solid waste is recycled, and better economic benefit is generated; the process method has better economic benefit for enterprises and great environmental protection benefit for society; the fluidity of the mixture is ensured by obtaining the mixture with the repose angle less than 39 degrees, so that the mixture is conveniently added into an electrolytic cell by a feeder and can be better dissolved in molten electrolyte; the current intensity and the addition amount of the mixture are set according to the required electrolysis speed, so that free control can be realized; so that the Gibbs free energy of the decomposition reaction formula of the harmful ingredients of the cyanide is far less than 0, the reaction is intensively carried out to the right, and the cyanide is decomposed in the aluminum electrolytic cell to generate N2And CO gas and electrolyte components NaF and Al2O3Can enter the electrolyte to realize cyclic utilization, realize harmlessness and reclamation; with Na3AlF6The electrolyte is recycled; product produced by birthThe aluminum-based alloy is kept in a liquid state and is deposited below electrolyte liquid, so that the aluminum-based alloy is convenient to collect; and the content of other components in the aluminum-based alloy can be adjusted by adjusting the proportion of the aluminum oxide so as to achieve various required alloy components.
Drawings
FIG. 1 is a flow chart of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
In the description of the present invention, it is to be understood that the terms "upper", "lower", "front", "rear", "left", "right", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention.
Referring to fig. 1, a method of electrolytically treating lining waste, includes the steps of:
s1: coarse crushing:
roughly crushing the removed waste lining material by using a jaw crusher; before coarse crushing, if caking with the diameter larger than 500mm exists, crushing the caking into small blocks by using a crust breaker so as to meet the inlet requirement of coarse crushing equipment, and then performing coarse crushing;
s2: grinding:
grinding the coarsely broken agglomerates by using a ball mill, wherein the grinding precision is set to be 150 microns;
s3: adjusting the content of alumina:
calculating according to the content of alumina in the ground lining waste, and adding industrial-grade alumina for mixing to enable the content of alumina in the mixture to reach 70-90%; so as to obtain a mixture with an repose angle less than 39 degrees, ensure the fluidity of the mixture, facilitate the addition of a feeder to an electrolytic cell, and better dissolve the mixture in the molten electrolyte;
the method for calculating the addition amount of the industrial alumina comprises the following steps:
setting, requiring Al in the mixture2O3The content reaches 80%, and the amount of lining waste is Q1, wherein Al2O3The content is x%, the quantity of the industrial-grade alumina to be supplemented is Q, and then
(Q1*x％+Q)/(Q1+Q)＝0.8
Q＝(4-5*x％)*Q1；
S4: preparing an electrolytic cell:
the anode and cathode of the electrolytic cell are made of carbon material, and the electrolyte is Na3AlF6；
S5: electrolysis:
adding the proportioned mixture into an electrolytic cell, setting the current intensity to be 100-700 KA, the voltage to be 3.5-3.8V and the electrolyte temperature to be 900-1000 ℃;
the current intensity of the electrolytic cell is matched with the addition amount of the mixture, and the calculation method comprises the following steps:
setting the current efficiency as 90% to calculate, firstly, calculating the electrochemical equivalent of the metal oxide in the raw material, and the formula is:
a ═ atomic weight/elemental valence/26.8, such as:
electrolytic Al2O3When Al is used, the electrochemical equivalent of Al is 26.98/3/26.8 ≈ 0.3356g/Ah
Electrolysis of SiO2When the electrochemical equivalent of Si is 28.08/4/26.8 ≈ 0.2619g/Ah
When electrolyzing MgO, the electrochemical equivalent of Mg is 24.3/2/26.8 ≈ 0.4534g/Ah
Etc.;
then, calculating the metal amount M capable of being produced per hour according to the electrochemical equivalent;
current intensity electrochemical equivalent current efficiency;
setting that the current intensity is 200kA, and calculating according to 90% current efficiency, calculating the corresponding metal amount produced per hour, such as:
the weight of Al produced per hour is
200*0.3356*90％＝60.408kg；
After the yield of the metal Al is calculated, the corresponding oxide Al is converted2O3Is added in an amount of 26.98 Al in terms of Al atomic weight2O3The molecular weight of (3) can be calculated as Al corresponding to 60.408kg of metallic Al2O3The amount of (A) is:
102*60.408/26.98≈228.377kg；
according to the calculation method, the mixture is added into the electrolytic cell by matching current;
s6: obtaining a finished product:
the harmful cyanide components in the lining waste are decomposed according to the following reaction formula:
6NaCN+2AlF3+9CO2＝6NaF+3N2+Al2O3+15CO
decomposing into harmless components;
the Gibbs free energy of this equation is related to temperature as shown in the following Table:
Figure BDA0002917394000000071
Figure BDA0002917394000000081
under the condition of the electrolysis temperature, the Gibbs free energy of the reaction formula is far less than 0, the reaction is strongly carried out to the right, cyanide is decomposed in an aluminum electrolysis cell to generate N2 and CO gas and electrolyte components NaF and Al2O3The electrolyte is recycled in the electrolyte, so that harmlessness and recycling are realized; with Na3AlF6The electrolyte is recycled;
at the same time, the oxides in the mix are reduced by carbon to metals such as:
2Al2O3+3C＝4Al+3CO2、
SiO2+C＝Si+CO2、
2Fe2O3+3C＝4Fe+3CO2、
2MgO+C＝2Mg+CO2
etc.;
in the electrolytic process, the produced aluminum-based alloy is kept in a liquid state and sinks below the electrolyte liquid because the aluminum-based alloy has higher density than the electrolyte;
finally, the aluminum-based alloy product with the aluminum content of more than 70 percent and other components of silicon, iron, magnesium and the like is obtained. Except that the content of aluminum is controlled by adding industrial-grade aluminum oxide, the content of other components is related to the components of the waste lining of the furnace. The content of other components in the aluminum-based alloy can be adjusted by adjusting the proportion of the aluminum oxide so as to achieve the required alloy components.
In the invention, after the lining powder is crushed, various compound components in the lining powder are decomposed into corresponding metals or other components under electrochemical and high-temperature conditions through electrolytic reaction, so that the resource utilization of valuable components is realized, and harmful components are decomposed into harmless components; compared with the method adopted and treated in the industry, the method can be used for direct landfill or landfill after harmless treatment, so that the extra cost and expenditure required by waste landfill are saved, the solid waste is recycled, and better economic benefit is generated. The process method has better economic benefit for enterprises and great environmental protection benefit for society. In the processing process, the lining waste is ground to 150 microns, and industrial-grade alumina is added, so that the content proportion of the alumina in the mixture reaches 70% -80%, the mixture with the repose angle smaller than 39 degrees is obtained, the fluidity of the mixture is ensured, the mixture is convenient to add into an electrolytic cell by a feeder and can be better dissolved in molten electrolyte; the current intensity and the addition amount of the mixture are set according to the required electrolysis speed, so that free control can be realized; the anode and the cathode of the electrolytic cell are made of carbon materials, the electrolyte is Na3AlF6, the set temperature is 900-100 ℃, so that Gibbs free energy of decomposition reaction formula of harmful ingredients of cyanide is far less than 0, the reaction is performed to the right strongly, and the cyanide is decomposed in the aluminum electrolytic cell to generate N2And CO gas and electrolyte components NaF andAl2O3can enter the electrolyte to realize cyclic utilization, realize harmlessness and reclamation; with Na3AlF6The electrolyte is recycled; the oxides in the mixture are reduced into metal by carbon; the produced aluminum-based alloy keeps liquid state and is deposited below electrolyte liquid, so that the aluminum-based alloy is convenient to collect; and the content of other components in the aluminum-based alloy can be adjusted by adjusting the proportion of the aluminum oxide so as to achieve various required alloy components.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (2)

1. A method of electrolytically treating lining waste comprising the steps of:
s1: roughly crushing, namely roughly crushing the removed waste lining material by using a jaw crusher;
s2: grinding, namely grinding the coarsely broken agglomerates by using a ball mill, wherein the grinding precision is set to be 150 microns;
s3: adjusting the content of alumina in the lining waste, calculating according to the content of alumina in the ground lining waste, adding industrial-grade alumina, and mixing to enable the content of alumina in the mixed material to reach 70-90%;
s4: preparing an electrolytic cell, wherein the anode and the cathode of the electrolytic cell are made of carbon materials, and the electrolyte is Na3AlF6；
S5: electrolyzing, namely adding the mixture after mixing and proportioning into an electrolytic bath, setting the current intensity to be 100-700 KA, the voltage to be 3.5-3.8V and the electrolyte temperature to be 900-1000 ℃;
s6: obtaining the aluminum-based alloy, decomposing harmful cyanide components into harmless components, and reducing metal oxides into metal components to obtain the aluminum-based alloy product.
2. The method of claim 1, wherein the demolished waste lining material is crushed into small pieces by a crust breaker to meet the inlet requirement of the rough-crushing device before the rough-crushing in step S1.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102011145A (en) * 2010-12-03 2011-04-13 伊川龙海科技实业有限公司 Method for recycling electrolytes and producing aluminum-silicon alloy as byproduct by using aluminum electrolysis waste mixing material
CN109913911A (en) * 2019-04-11 2019-06-21 中南大学 The processing method of alumina-silica solid waste in a kind of aluminum cell waste liner
RU2716727C1 (en) * 2019-08-16 2020-03-16 Федеральное государственное бюджетное учреждение науки Институт высокотемпературной электрохимии Уральского отделения Российской Академии наук Electrolytic method of producing aluminum ligatures from oxide material
CN111455407A (en) * 2020-04-15 2020-07-28 中南大学 Method for treating cyanide in overhaul slag of aluminum electrolytic cell

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102011145A (en) * 2010-12-03 2011-04-13 伊川龙海科技实业有限公司 Method for recycling electrolytes and producing aluminum-silicon alloy as byproduct by using aluminum electrolysis waste mixing material
CN109913911A (en) * 2019-04-11 2019-06-21 中南大学 The processing method of alumina-silica solid waste in a kind of aluminum cell waste liner
RU2716727C1 (en) * 2019-08-16 2020-03-16 Федеральное государственное бюджетное учреждение науки Институт высокотемпературной электрохимии Уральского отделения Российской Академии наук Electrolytic method of producing aluminum ligatures from oxide material
CN111455407A (en) * 2020-04-15 2020-07-28 中南大学 Method for treating cyanide in overhaul slag of aluminum electrolytic cell

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
WENYUAN HOU等: "Recycling of spent refractory materials to produce Al-Si master alloys via the aluminum reduction cell", JOURNAL OF CLEANER PRODUCTION, vol. 289, pages 1 - 2 *
侯文渊 等: "铝电解槽协同处置废耐火材料的工业试验研究", 中南大学学报（自然科学版）, vol. 54, no. 2, pages 587 - 594 *

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