CN111499397A - Method for preparing reclaimed materials of aluminum oxide and silicon oxide by using electrolytic bath aluminum-silicon overhaul residues - Google Patents

Method for preparing reclaimed materials of aluminum oxide and silicon oxide by using electrolytic bath aluminum-silicon overhaul residues Download PDF

Info

Publication number
CN111499397A
CN111499397A CN202010294361.7A CN202010294361A CN111499397A CN 111499397 A CN111499397 A CN 111499397A CN 202010294361 A CN202010294361 A CN 202010294361A CN 111499397 A CN111499397 A CN 111499397A
Authority
CN
China
Prior art keywords
aluminum
oxide
silicon
alumina
particle size
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010294361.7A
Other languages
Chinese (zh)
Other versions
CN111499397B (en
Inventor
李贺松
侯文渊
冯源
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central South University
Original Assignee
Central South University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Central South University filed Critical Central South University
Priority to CN202010294361.7A priority Critical patent/CN111499397B/en
Publication of CN111499397A publication Critical patent/CN111499397A/en
Application granted granted Critical
Publication of CN111499397B publication Critical patent/CN111499397B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62204—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products using waste materials or refuse
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • 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
    • C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5427—Particle size related information expressed by the size of the particles or aggregates thereof millimeter or submillimeter sized, i.e. larger than 0,1 mm
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

The invention provides a method for preparing a reclaimed material of aluminum oxide and silicon oxide by using electrolytic bath aluminum-silicon overhaul residues, which comprises the following steps: A) crushing the hardened anti-seepage material, the insulating brick and the refractory brick in the aluminum-silicon overhaul slag to obtain an initial raw material; B) mixing and reacting the initial raw material with an aqueous solution of an oxidant to remove cyanide in the initial raw material to obtain a treatment solution; C) and mixing the treatment solution with an inhibitor and a trapping agent for flotation, introducing bubbles, and sequentially performing bubble scraping, washing and drying to obtain the reclaimed materials of the aluminum oxide and the silicon oxide. The invention utilizes a flotation method to separate the cryolite from the alumina and the silicon oxide, and then takes the alumina and the silicon oxide as ingredients to prepare the dry type impermeable material, and simultaneously completes the direct recovery of the insulating brick and the refractory brick with relatively complete components and the regeneration treatment of the overhaul slag solid waste.

Description

Method for preparing reclaimed materials of aluminum oxide and silicon oxide by using electrolytic bath aluminum-silicon overhaul residues
Technical Field
The invention relates to the technical field of aluminum electrolysis overhaul residues, in particular to a method for preparing a reclaimed material of aluminum oxide and silicon oxide by using electrolytic bath aluminum-silicon overhaul residues.
Background
China is a big country for manufacturing aluminum industry, and the yield of alumina and electrolytic aluminum accounts for more than 40 percent of the world. In the aluminum production process, a large amount of hazardous waste, commonly called overhaul residue, is generated. In recent years, with the increasing requirements of the national environmental protection, a great deal of aluminum electrolysis industryThe waste residue treatment problem becomes the first problem to be solved by related enterprises, and an economical and feasible waste residue utilization new technology is urgently needed to be provided. In the aluminum electrolysis industry at present, the common electrolytic bath overhaul residues are aluminum-silicon overhaul residues, and the sources of the aluminum-silicon overhaul residues are light castable, ceramic fiber plates, clay heat-insulating refractory bricks, dry type impermeable materials, high-aluminum refractory bricks, high-strength castable, impermeable bricks and other materials in the electrolytic bath. The overhaul slag contains a large amount of pollutant components, but also contains a plurality of useful components; for the aluminum-silicon overhaul slag, the solid waste contains SiO2、Al2O3、TiO2、Fe2O3The output of the waste residues is up to hundreds of millions of tons every year, the waste residues are not utilized and can only be treated by adopting a stacking method, and serious environmental pollution is caused.
In the aluminum electrolysis production, an anti-seepage material is required to be arranged in the aluminum electrolysis cell, is used for preventing the leakage of high-temperature aluminum liquid and electrolyte for the aluminum electrolysis, and is also an important component of a refractory and heat-insulating material of the aluminum electrolysis cell. At present, the main components of the impermeable material adopted in the industry are SiO2And Al2O3The principle is that when electrolyte permeates and contacts with the impermeable material, the electrolyte reacts with the impermeable material to generate a compact vitreous body-shaped nepheline layer, so that electrolyte liquid and Na and NaF steam are prevented from continuously permeating, the heat-insulating layer is prevented from being damaged, the occurrence of leakage accidents is prevented, the safety production is guaranteed, the service life of the aluminum electrolytic cell is prolonged, and the economic benefit is improved.
Part of the seepage-proofing material in the aluminum-silicon solid waste reacts with electrolyte to form hard lumps, and the rest seepage-proofing material is well preserved with insulating bricks and refractory bricks, which are treated as dangerous waste to cause resource waste.
The scholars propose to regenerate the anti-seepage material by using the waste cell lining of the aluminum electrolysis cell, for example, the Chinese patent with the publication number of CN105130460A proposes a method for regenerating the anti-seepage material by using the waste cell lining of the aluminum electrolysis cell. The method sorts the waste cathode carbon blocks, refractory materials and waste cathode steel bars in the waste cell lining of the aluminum electrolytic cell according to the types, selects the refractory materials in the waste cathode carbon blocks, refractory materials and waste cathode steel bars, crushes the refractory materials into powder, and adds alumina, calcium oxide and the like to mix to prepare the regenerated anti-seepage material. However, the method does not remove the electrolyte in the waste refractory material, the content of the electrolyte is about 40-50%, and when the electrolyte is used as a raw material for manufacturing the anti-seepage material, the content of alumina and silicon oxide playing the role of anti-seepage is reduced, so that the anti-seepage effect is influenced.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing reclaimed materials of aluminum oxide and silicon oxide by using electrolytic bath aluminum-silicon overhaul residues, the method can realize the reuse of the overhaul residues and can prepare reclaimed materials of the aluminum oxide and the silicon oxide, and the reclaimed materials can be used as components of dry type impermeable materials.
In view of the above, the present application provides a method for preparing a reclaimed material of aluminum oxide and silicon oxide from an electrolytic bath aluminum-silicon overhaul slag, comprising the following steps:
A) crushing the hardened anti-seepage material, the insulating brick and the refractory brick in the aluminum-silicon overhaul slag to obtain an initial raw material;
B) mixing and reacting the initial raw material with an aqueous solution of an oxidant to remove cyanide in the initial raw material to obtain a treatment solution;
C) and mixing the treatment solution with an inhibitor and a trapping agent for flotation, introducing bubbles, and sequentially performing bubble scraping, washing and drying to obtain the reclaimed materials of the aluminum oxide and the silicon oxide.
Preferably, the particle size of the starting material is not greater than 200 μm.
Preferably, the particle size of the starting material is 150 to 200 μm.
Preferably, the aqueous solution of the oxidant contains sodium hydroxide and one or two of sodium hypochlorite and hydrogen peroxide, and the pH of the aqueous solution of the oxidant is more than 10; and the content of one or two of the sodium hypochlorite and the hydrogen peroxide in the oxidant aqueous solution is 20-30 wt%.
Preferably, the ratio of the starting material to the aqueous solution of the oxidizing agent is 1 g: (2-6) ml.
Preferably, the collector is selected from one or more of oxidized paraffin soap, dicarboxyethyl sulfosuccinamide tetrasodium salt and silicone oil, and the inhibitor is selected from one or more of sodium oxalate, sodium citrate and sodium carboxymethyl cellulose.
The application provides a dry impermeable material, which consists of a reclaimed material of alumina and silica, quartz sand, alumina, calcium oxide and magnesium oxide prepared by the method in the scheme.
Preferably, the reclaimed materials account for 30-55 wt%, the quartz sand accounts for 25-35 wt%, the alumina accounts for 10-20 wt%, the calcium oxide accounts for 5-10 wt%, and the magnesium oxide accounts for 3-8 wt%.
Preferably, the particle size of the reclaimed materials is less than 200 mu m, the particle size of the quartz sand is 2.5-5 mm, the particle size of the aluminum oxide is 0.5-2.5 mm, the particle size of the calcium oxide is 0.5-2.5 mm, and the content of the magnesium oxide is 0.5-2.0 mm.
The application provides a method for preparing a reclaimed material of alumina and silica by using electrolytic bath aluminum-silicon overhaul residues, which separates cryolite from the alumina and the silica in the overhaul residues by using a flotation method, thereby preparing the reclaimed material of the alumina and the silica. The reclaimed material can be used as a batching for further preparing a dry impermeable material. The method provided by the application not only prepares the anti-seepage material, but also solves the problems of environmental pollution caused by the overhaul slag solid waste and economic value generated by recycling the solid waste in the aluminum electrolysis industry.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
The method for preparing the reclaimed materials of aluminum oxide and silicon oxide by using the electrolytic bath aluminum-silicon overhaul slag solves the problems of environmental pollution and solid waste reutilization caused by overhaul slag solid waste and impermeable materials in the aluminum electrolysis industry, and particularly, the method for preparing the reclaimed materials of aluminum oxide and silicon oxide by using the electrolytic bath aluminum-silicon overhaul slag comprises the following steps:
A) crushing the hardened anti-seepage material, the insulating brick and the refractory brick in the aluminum-silicon overhaul slag to obtain an initial raw material;
B) mixing and reacting the initial raw material with an aqueous solution of an oxidant to remove cyanide in the initial raw material to obtain a treatment solution;
C) and mixing the treatment solution with an inhibitor and a trapping agent for flotation, introducing bubbles, and sequentially performing bubble scraping, washing and drying to obtain the reclaimed materials of the aluminum oxide and the silicon oxide.
In the process of preparing the reclaimed materials of the alumina and the silica by using the aluminum-silicon overhaul residues of the electrolytic cell, firstly, a hardened anti-seepage material, a heat-insulating brick and a refractory brick in the aluminum-silicon overhaul residues are selected as raw materials of the reclaimed materials of the alumina and the silica, and the raw materials are mixed and crushed to obtain initial raw materials; in the present application, the particle size of the primary raw material is not greater than 200 μm, and in a specific embodiment, the particle size of the primary raw material is 150 to 200 μm. The crushing is a crushing method well known to those skilled in the art, and the present application is not particularly limited, and in a specific embodiment, the crushing is performed by using a ball mill.
The application then mixes and reacts the initial raw material with the aqueous solution of the oxidant to remove the cyanide in the initial raw material; the oxidant is used for removing cyanide in the initial raw material; in a specific embodiment, the aqueous solution of the oxidant contains sodium hydroxide and one or two of sodium hypochlorite and hydrogen peroxide, and the pH of the aqueous solution of the oxidant is more than 10; the content of one or two of the sodium hypochlorite and the hydrogen peroxide in the oxidant aqueous solution is 20-30 wt%; the sodium hydroxide in the aqueous solution of the oxidizing agent is used to adjust the pH of the aqueous solution to a pH above 10 to ensure cyanide oxidation.
Mixing the treated solution with an inhibitor and a trapping agent for flotation, introducing bubbles, and sequentially performing bubble scraping, washing and drying to obtain a reclaimed material of aluminum oxide and silicon oxide; in the flotation process, the trapping agent is used for enabling the surface of the mineral to be easily combined with the bubbles, improving the floatability of the mineral and enabling the mineral to be easily attached to the bubbles. The inhibitor is used for inhibiting the combination of non-target minerals and bubbles, and reducing the floatability of the minerals. The inhibitor and the capture agent are obtained by analyzing the physical and chemical properties of the electrolyte and the carbon powder; the collector is selected from one or more of oxidized paraffin soap, dicarboxyethyl succinamide tetrasodium salt and silicone oil, and the inhibitor is selected from one or more of sodium oxalate, sodium citrate and sodium carboxymethyl cellulose. The above-mentioned processes of foam scraping, water washing and drying are technical means well known to those skilled in the art, and the present application is not particularly limited.
After the reclaimed materials of the alumina and the silicon oxide are obtained, the reclaimed materials are used as the components of the dry impermeable material and are mixed with quartz sand, the alumina, the calcium oxide and the magnesium oxide to obtain the dry impermeable material.
Because the main component of the anti-seepage material is SiO2And Al2O3React with electrolyte to form Na2O·Al2O3·2SiO2Therefore, in order to maximize the effect of the anti-seepage material, SiO in the materials2With Al2O3The proportion should be in the range of 2: around 1. In view of this, the reclaimed material is 30 to 55 wt%, the quartz sand is 25 to 35 wt%, the alumina is 10 to 20 wt%, the calcium oxide is 5 to 10 wt%, and the magnesium oxide is 3 to 8 wt%.
The particle sizes of the reclaimed materials of the alumina and the silicon oxide, the quartz sand, the alumina, the calcium oxide and the magnesium oxide also influence the seepage-proofing effect of the seepage-proofing material; in a specific embodiment, the particle size of the reclaimed material is less than 200 μm, the particle size of the quartz sand is 2.5-5 mm, the particle size of the aluminum oxide is 0.5-2.5 mm, the particle size of the calcium oxide is 0.5-2.5 mm, and the content of the magnesium oxide is 0.5-2.0 mm.
The application provides a novel treatment method of overhaul residues, namely a method for preparing reclaimed materials of aluminum oxide and silicon oxide by using electrolytic bath aluminum-silicon overhaul residues, which comprises the steps of firstly removing well-preserved impermeable materials, insulating bricks and refractory bricks by a flotation method and recycling; and crushing the other part of the overhaul slag, and then adding a reagent for treatment to obtain a dry anti-seepage material raw material for preparing the anti-seepage material.
For further understanding of the present invention, the method for preparing a barrier material by using an electrolytic bath aluminum siliceous overhaul slag provided by the present invention is described in detail below with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example 1
1) Selecting hardened anti-seepage materials positioned at the lower part of a cathode in the aluminum-silicon overhaul residues, well-preserved insulating bricks and refractory bricks, and crushing the materials by using a ball mill until the particle size of the powder is 150-200 microns;
2) preparing an aqueous solution with the sodium hypochlorite content of 25%, and simultaneously adding NaOH into the aqueous solution to ensure that the pH value of the aqueous solution is about 13 to obtain an oxidant aqueous solution;
3) mixing the particles obtained in step 1) with the aqueous solution of an oxidizing agent obtained in step 2) in a ratio of 1: 3, proportioning, mixing and stirring for two hours; NaOH is added into the aluminum silicon overhaul slag during stirring to ensure that the pH value is always above 10 in the whole process, and the purpose of the step is to remove cyanide in the aluminum silicon overhaul slag;
4) adding an inhibitor and a trapping agent into the treated solution, wherein the collecting agent is oxidized paraffin soap, the inhibitor is sodium oxalate, stirring uniformly, introducing bubbles, and sequentially scraping, washing and drying to obtain an aluminum oxide and silicon oxide reclaimed material; the recovered material contains about 53% of silicon oxide, 96.5% of aluminum oxide and silicon oxide, and 3.5% of impurities
5) Mixing the prepared reclaimed materials with quartz sand, aluminum oxide, calcium oxide and magnesium oxide according to a proportion, wherein the specific proportion and the granularity requirement are as follows:
Figure BDA0002451622200000061
and pouring the materials into a stirrer, and uniformly mixing to obtain the dry impermeable material.
SiO in the impermeable material prepared by the method2And Al2O3The content is more than 85 percent, the tap density is 1.97g/cm3, and the bulk density is1.60g/cm3, the electrolyte penetration resistance under the experimental condition of 96h is within 15mm, and the thermal conductivity at 600 ℃ is 0.43W/m.
Example 2
1) Selecting hardened anti-seepage materials positioned at the lower part of a cathode in the aluminum-silicon overhaul residues, well-preserved insulating bricks and refractory bricks, and crushing the materials by using a ball mill until the particle size of the powder is 150-200 microns;
2) preparing an aqueous solution with the hydrogen peroxide content of 20%, and simultaneously adding NaOH into the aqueous solution to ensure that the pH value is about 12 to obtain an oxidant aqueous solution;
3) mixing the particles obtained in step 1) with an aqueous solution of an oxidizing agent in a ratio of 1: 6, proportioning, mixing and stirring for two hours; NaOH is added into the aluminum silicon overhaul slag during stirring to ensure that the pH value is always above 11 in the whole process, and the purpose of the step is to remove cyanide in the aluminum silicon overhaul slag;
4) adding an inhibitor and a trapping agent into the treated solution, wherein the collecting agent is dicarboxyethyl succinamide sulfide tetrasodium salt, the inhibitor is sodium oxalate and sodium carboxymethyl cellulose, uniformly stirring, introducing bubbles, and sequentially scraping, washing and drying to obtain an aluminum oxide and silicon oxide reclaimed material; the content of silicon oxide is about 56 percent, the total purity of aluminum oxide and silicon oxide is 97.2 percent, and the content of impurities is 2.8 percent
5) Mixing the prepared reclaimed materials with quartz sand, aluminum oxide, calcium oxide and magnesium oxide according to a proportion, wherein the specific proportion and the granularity requirement are as follows:
Figure BDA0002451622200000062
Figure BDA0002451622200000071
and pouring the materials into a stirrer, and uniformly mixing to obtain the dry impermeable material.
SiO in the impermeable material prepared by the method2And Al2O3The content is more than 85 percent, the tap density is 1.87g/cm3, the bulk density is 1.51g/cm3, and the electrolyte permeation resistance is 15mm or more under the experimental condition of 96 hoursAnd a thermal conductivity of 0.37W/m at 600 ℃.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (9)

1. A method for preparing reclaimed materials of aluminum oxide and silicon oxide by using electrolytic bath aluminum-silicon overhaul residues comprises the following steps:
A) crushing the hardened anti-seepage material, the insulating brick and the refractory brick in the aluminum-silicon overhaul slag to obtain an initial raw material;
B) mixing and reacting the initial raw material with an aqueous solution of an oxidant to remove cyanide in the initial raw material to obtain a treatment solution;
C) and mixing the treatment solution with an inhibitor and a trapping agent for flotation, introducing bubbles, and sequentially performing bubble scraping, washing and drying to obtain the reclaimed materials of the aluminum oxide and the silicon oxide.
2. The method of claim 1, wherein the particle size of the starting material is no greater than 200 μm.
3. The method according to claim 1 or 2, wherein the particle size of the starting material is 150 to 200 μm.
4. The method of claim 1, wherein the aqueous solution of the oxidizing agent comprises sodium hydroxide and one or both of sodium hypochlorite and hydrogen peroxide, and has a pH > 10; and the content of one or two of the sodium hypochlorite and the hydrogen peroxide in the oxidant aqueous solution is 20-30 wt%.
5. The method according to claim 4, characterized in that the ratio of the initial charge to the aqueous solution of the oxidizing agent is 1 g: (2-6) ml.
6. The method of claim 1 wherein the collector is selected from one or more of oxidized paraffin soap, dicarboxyethyl sulfosuccinamamide tetrasodium salt, and silicone oil and the inhibitor is selected from one or more of sodium oxalate, sodium citrate, and sodium carboxymethylcellulose.
7. A dry impermeable material, which consists of recycled alumina and silica prepared by the method of any one of claims 1 to 6, quartz sand, alumina, calcium oxide and magnesium oxide.
8. The dry type impermeable material according to claim 7, wherein the reclaimed material is 30-55 wt%, the quartz sand is 25-35 wt%, the alumina is 10-20 wt%, the calcium oxide is 5-10 wt%, and the magnesium oxide is 3-8 wt%.
9. The dry type impermeable material according to claim 7, characterized in that the reclaimed material has a particle size of less than 200 μm, the quartz sand has a particle size of 2.5-5 mm, the alumina has a particle size of 0.5-2.5 mm, the calcium oxide has a particle size of 0.5-2.5 mm, and the magnesium oxide has a content of 0.5-2.0 mm.
CN202010294361.7A 2020-04-15 2020-04-15 Method for preparing reclaimed materials of aluminum oxide and silicon oxide by using electrolytic bath aluminum-silicon overhaul residues Active CN111499397B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010294361.7A CN111499397B (en) 2020-04-15 2020-04-15 Method for preparing reclaimed materials of aluminum oxide and silicon oxide by using electrolytic bath aluminum-silicon overhaul residues

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010294361.7A CN111499397B (en) 2020-04-15 2020-04-15 Method for preparing reclaimed materials of aluminum oxide and silicon oxide by using electrolytic bath aluminum-silicon overhaul residues

Publications (2)

Publication Number Publication Date
CN111499397A true CN111499397A (en) 2020-08-07
CN111499397B CN111499397B (en) 2021-04-09

Family

ID=71866367

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010294361.7A Active CN111499397B (en) 2020-04-15 2020-04-15 Method for preparing reclaimed materials of aluminum oxide and silicon oxide by using electrolytic bath aluminum-silicon overhaul residues

Country Status (1)

Country Link
CN (1) CN111499397B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113173777A (en) * 2021-03-24 2021-07-27 湖南国发控股有限公司 Formula and process method for preparing ceramsite by using overhaul residues
CN114988892A (en) * 2022-05-21 2022-09-02 郑州大学 Method for preparing dry type impermeable material by using overhaul slag clinker
CN115849945A (en) * 2022-10-18 2023-03-28 阿坝铝厂 Treatment process of aluminum electrolysis cell overhaul slag

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4425309A (en) * 1982-05-13 1984-01-10 David Weston Production of a purified alumina-silica product and substantially pure aluminum trichloride from bauxites and clays
EP1508762B1 (en) * 1999-12-09 2007-05-30 MOLTECH Invent S.A. Refractory material for use at high temperatures
CN101054693A (en) * 2007-05-31 2007-10-17 中国铝业股份有限公司 Method of extracting electrolyte from waste cathode carbon block of aluminum electrolysis bath
CN102009062A (en) * 2010-12-03 2011-04-13 伊川龙海科技实业有限公司 Recycling method of waste dry-type aluminum electrolytic anti-seepage material
CN102560591A (en) * 2011-12-01 2012-07-11 浙江吉利汽车研究院有限公司 Micro-arc oxidation electrolyte and micro-arc oxidation method
US8236452B2 (en) * 2009-11-02 2012-08-07 Nanotek Instruments, Inc. Nano-structured anode compositions for lithium metal and lithium metal-air secondary batteries
CN104894382A (en) * 2015-06-03 2015-09-09 东北大学 Recovery treatment method of electrolytic aluminum ash and refractory material lining waste
CN105130460A (en) * 2015-07-11 2015-12-09 云南云铝润鑫铝业有限公司 Method of regenerating anti-seepage material from waste aluminium electrolytic tank lining
CN106433850A (en) * 2016-09-21 2017-02-22 红河学院 Method for preparing cement kiln fuel from aluminium electrolysis waste cathodes
CN107626712A (en) * 2017-08-29 2018-01-26 陕西三秦能源长宏铝业有限公司 A kind of aluminium electroloysis danger solid waste integrated conduct method and recycling
CN107720723A (en) * 2017-11-09 2018-02-23 北京科技大学 A kind of method of overall treatment aluminium electrolytic tank
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
CN109909272A (en) * 2019-04-11 2019-06-21 新疆新能源(集团)准东环境发展有限公司 The process for the treatment of of wastes with processes of wastes against one another harmless treatment aluminium cell slag from delining
CN110129565A (en) * 2019-05-15 2019-08-16 东北大学 The method for producing Antaciron as raw material coreless armature feeding using aluminium ash
US10615403B2 (en) * 2015-05-30 2020-04-07 Alpha-En Corporation High purity lithium and associated products and processes

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4425309A (en) * 1982-05-13 1984-01-10 David Weston Production of a purified alumina-silica product and substantially pure aluminum trichloride from bauxites and clays
EP1508762B1 (en) * 1999-12-09 2007-05-30 MOLTECH Invent S.A. Refractory material for use at high temperatures
CN101054693A (en) * 2007-05-31 2007-10-17 中国铝业股份有限公司 Method of extracting electrolyte from waste cathode carbon block of aluminum electrolysis bath
US8236452B2 (en) * 2009-11-02 2012-08-07 Nanotek Instruments, Inc. Nano-structured anode compositions for lithium metal and lithium metal-air secondary batteries
CN102009062A (en) * 2010-12-03 2011-04-13 伊川龙海科技实业有限公司 Recycling method of waste dry-type aluminum electrolytic anti-seepage material
CN102560591A (en) * 2011-12-01 2012-07-11 浙江吉利汽车研究院有限公司 Micro-arc oxidation electrolyte and micro-arc oxidation method
US10615403B2 (en) * 2015-05-30 2020-04-07 Alpha-En Corporation High purity lithium and associated products and processes
CN104894382A (en) * 2015-06-03 2015-09-09 东北大学 Recovery treatment method of electrolytic aluminum ash and refractory material lining waste
CN105130460A (en) * 2015-07-11 2015-12-09 云南云铝润鑫铝业有限公司 Method of regenerating anti-seepage material from waste aluminium electrolytic tank lining
CN106433850A (en) * 2016-09-21 2017-02-22 红河学院 Method for preparing cement kiln fuel from aluminium electrolysis waste cathodes
CN107626712A (en) * 2017-08-29 2018-01-26 陕西三秦能源长宏铝业有限公司 A kind of aluminium electroloysis danger solid waste integrated conduct method and recycling
CN107720723A (en) * 2017-11-09 2018-02-23 北京科技大学 A kind of method of overall treatment aluminium electrolytic tank
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
CN109909272A (en) * 2019-04-11 2019-06-21 新疆新能源(集团)准东环境发展有限公司 The process for the treatment of of wastes with processes of wastes against one another harmless treatment aluminium cell slag from delining
CN110129565A (en) * 2019-05-15 2019-08-16 东北大学 The method for producing Antaciron as raw material coreless armature feeding using aluminium ash

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李楠: "浮选法分离铝电解废旧阴极中的碳和电解质", 《轻金属》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113173777A (en) * 2021-03-24 2021-07-27 湖南国发控股有限公司 Formula and process method for preparing ceramsite by using overhaul residues
CN114988892A (en) * 2022-05-21 2022-09-02 郑州大学 Method for preparing dry type impermeable material by using overhaul slag clinker
CN115849945A (en) * 2022-10-18 2023-03-28 阿坝铝厂 Treatment process of aluminum electrolysis cell overhaul slag
CN115849945B (en) * 2022-10-18 2024-02-09 阿坝铝厂 Treatment process of aluminum electrolysis cell overhaul slag

Also Published As

Publication number Publication date
CN111499397B (en) 2021-04-09

Similar Documents

Publication Publication Date Title
CN111499397B (en) Method for preparing reclaimed materials of aluminum oxide and silicon oxide by using electrolytic bath aluminum-silicon overhaul residues
CN101811695B (en) Method for recovering graphite from electrolytic aluminum waste cathode carbon block
CN110106312B (en) Process for producing LF (ladle furnace) slagging agent by using electrolytic aluminum carbon slag
CN103343363B (en) The electrolytical production method of a kind of electrolgtic aluminium
CN110016557B (en) Method for preparing ferro-silicon-aluminum by smelting aluminum ash serving as raw material in electric arc furnace
CN110878385B (en) Method for producing molten steel precipitation deoxidizer by using electrolytic aluminum carbon slag
CN101480658A (en) Method for electrolyzing waste and old cathode carbon block by comprehensive utilization of aluminum
CN105964660B (en) A kind of method of harmless treatment aluminium electrolytic tank
CN110129506B (en) Method for preparing ferro-silicon-aluminum alloy by carbon thermal reduction of waste refractory material pretreatment
CN101988209A (en) Method for treating discarded silicon carbide side wall material of aluminum electrolytic cell
CN111206257B (en) Alkaline waste residue dealkalization method based on electrochemistry
CN110129565B (en) Method for preparing ferrosilicon alloy by feeding aluminum ash as raw material through hollow electrode
CN110117718B (en) Method for smelting and preparing ferro-silicon-aluminum by using waste refractory material as raw material in electric arc furnace
CN102010932B (en) Method for producing deoxidizer by utilizing waste silicon carbide of aluminium electrolysis
CN110016565B (en) Method for preparing ferro-silicon-aluminum alloy by feeding hollow electrode with waste refractory material as raw material
CN114074949B (en) Catalytic dissociation method for fluoride in waste material of electrolytic tank
CN109133028A (en) A method of electrolytic cell waste cathode carbon block recycling is disposed with alkaline process
CN105018739A (en) Efficient and comprehensive aluminium ash recycling method
CN111072393B (en) Environment-friendly dry type impermeable material suitable for aluminum electrolytic cell
CN110004300B (en) Method for preparing ferrosilicon alloy by using aluminum ash as raw material through plasma jet feeding
CN111455407A (en) Method for treating cyanide in overhaul slag of aluminum electrolytic cell
CN105130460A (en) Method of regenerating anti-seepage material from waste aluminium electrolytic tank lining
CN109609776A (en) A method of copper cobalt in copper vessel slag is extracted using waste cathode of aluminum electrolytic cell carbon block
CN110029227B (en) Method for preparing ferro-silicon-aluminum by using waste refractory material as raw material through plasma jet feeding
CN114032401A (en) Composition for removing recycled brass smelting furnace deposit, ditch cleaning agent and method for removing recycled brass smelting furnace deposit

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant