CN110820017B - Preparation method of aluminum-manganese alloy - Google Patents
Preparation method of aluminum-manganese alloy Download PDFInfo
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Abstract
The invention provides a preparation method of an aluminum-manganese alloy, which comprises the following steps: the method comprises the following steps: A) crushing the aluminum-silicon overhaul residues to obtain a crushed material, wherein the aluminum content in the crushed material is 15-20 wt%, and the iron content is less than or equal to 5 wt%; B) mixing a manganese-rich source, aluminum oxide and the crushed materials, and then feeding the mixture into an electrolytic cell for electrolysis to obtain an aluminum-manganese alloy; the electrolyte superheat degree of the electrolysis is 9-13 ℃. The method for preparing the aluminum-manganese alloy by using the electrolysis method obtains the aluminum-manganese alloy with more stable chemical property and higher purity, and prepares the aluminum-manganese alloy by using the overhaul slag solid waste which is generated by the electrolytic aluminum industry and is harmful to the environment, so that the environmental problem of solid waste stockpiling is solved, and the solid waste is reused, thereby bringing direct economic value.
Description
Technical Field
The invention relates to the technical field of recycling of aluminum-silicon overhaul residues, in particular to a preparation method of an aluminum-manganese alloy.
Background
China is a big aluminum manufacturing country, and the yield of alumina and electrolytic aluminum accounts for more than 40 percent of the world. High-quality bauxite resources are deficient and can not meet the development requirement of the aluminum industry in China, and more than 50% of bauxite needs to be imported, so that the development of the aluminum industry in China is severely restricted. Therefore, actively developing the non-traditional aluminum mineral to produce metal aluminum and developing a new aluminum smelting method has important significance for increasing the domestic aluminum resource supply and promoting the sustainable development of the aluminum industry.
With the continuous improvement of the national environmental protection requirement in recent years, the problem of processing a large amount of waste residues in the aluminum electrolysis industry becomes the first problem to be solved by related enterprises, and an economical and feasible new waste residue utilization technology is urgently needed to be provided. In the aluminum electrolysis industry, the aluminum-silicon solid waste in the electrolytic bath overhaul residues, namely the aluminum-silicon overhaul residues, are generally prepared from a large amount of pollutant components in the material overhaul residues such as light castable, ceramic fiber board, clay heat-insulating refractory brick, dry impermeable material, high-aluminum refractory brick, high-strength castable, impermeable brick and the like in the electrolytic bath, but the pollutant components also contain a large amount of useful components. For aluminum-silicon overhaul slag, consolidationThe 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 only can be treated by adopting a stacking method, so that the serious environmental pollution is caused.
At present, the industries all develop application research of related waste residues; for example: the waste residues are used as raw materials, the aluminum-manganese alloy is prepared through carbon electrothermal reduction, then the aluminum-manganese alloy for casting is prepared by using the aluminum-manganese alloy as the raw materials, the aluminum-manganese alloy takes manganese as a main component, the content of the manganese is 1.0-15%, the aluminum-manganese alloy has good antirust capacity, and the aluminum-manganese alloy is often applied to humid environments such as external packages, mechanical parts, refrigerators, air-conditioning ventilation pipelines and the like. But the method limits the application of the technology for treating the waste residue containing aluminum and silicon by the carbon electrothermal method because the impurity content in the aluminum-manganese alloy produced by the method is higher.
The method for preparing the aluminum-manganese alloy at the present stage mainly comprises a smelting reduction method and a carbothermic reduction method, wherein the smelting reduction method needs to remove an oxide film on the surface of powder by using a chemical reagent from mixed powder containing manganese and aluminum, and then put the mixed powder into a reaction furnace for high-temperature smelting reduction, and the method has the advantages of complex process, energy waste and high burning loss rate; the carbothermic process has high energy consumption and high requirements for equipment. In view of this, it is necessary to prepare the aluminum-manganese alloy with high purity, low impurity content and stable chemical property by using the aluminum electrolysis waste slag.
Disclosure of Invention
The invention aims to provide a preparation method of an aluminum-manganese alloy, which utilizes aluminum-silicon overhaul slag to prepare the aluminum-manganese alloy with high purity, low impurity content and stable chemical property.
In view of the above, the present application provides a method for preparing an aluminum-manganese alloy, including the following steps:
A) crushing the aluminum-silicon overhaul residues to obtain a crushed material, wherein the aluminum content in the crushed material is 15-20 wt%, and the iron content is less than or equal to 5 wt%;
B) mixing a manganese-rich source, aluminum oxide and the crushed materials, and then feeding the mixture into an electrolytic cell for electrolysis to obtain an aluminum-manganese alloy; the electrolyte superheat degree of the electrolysis is 9-13 ℃.
Preferably, the manganese-rich source is selected from one or more of manganese-rich slag, manganese oxide, manganese roselle, manganese garnet and manganese olivine.
Preferably, the manganese-rich source is manganese-rich slag, and the manganese-rich slag contains 20-30 wt% of manganese, 3-3.5 wt% of iron and 0.01-0.05 wt% of phosphorus.
Preferably, the electrolyte for electrolysis is cryolite-based molten salt, and comprises 2.10-3.35 wt% of magnesium fluoride, 1.35-2.55 wt% of lithium fluoride, 3.00-5.45 wt% of calcium fluoride, 1.00-2.40 wt% of potassium fluoride, 1.00-3.30 wt% of alumina, 0.10-1.50 wt% of manganese dioxide and the balance cryolite.
Preferably, the electrolytic electrolyte also comprises 1.26-3.34 wt% of spodumene and 2.37-3.12 wt% of boride.
Preferably, the molecular ratio of sodium fluoride to aluminum fluoride in the cryolite-based molten salt is (2.3-2.6): 1.
preferably, the crushing process in the step a) is specifically as follows:
feeding the aluminum-silicon overhaul slag into a jaw crusher for primary crushing, feeding the obtained initial material into a reaction hammer crusher for secondary crushing, feeding the obtained material into a vertical pulverizer, and sieving to obtain a crushed material;
the grain diameter of the materials after the re-crushing is less than or equal to 5mm, and the grain diameter of the crushed materials is less than or equal to 0.15 mm.
Preferably, the content of the manganese-rich source in a mixed material obtained by mixing the manganese-rich source, the alumina and the crushed material is 10-20 wt%, the content of the crushed material is 5-50 wt%, and the balance is the alumina.
Preferably, when the content of the crushed materials is 5-20 wt%, the electrolysis temperature of electrolysis is 910-930 ℃, and when the content of the crushed materials is 21-50 wt%, the electrolysis temperature of electrolysis is 950-960 ℃; the electrolytic voltage of the electrolysis is 4.0-4.2V, and the current efficiency is 85-94%.
Preferably, the aluminum content in the aluminum-manganese alloy is 80-95 wt%, and the manganese content is 3-14 wt%.
The application provides a preparation method of an aluminum-manganese alloy, which comprises the steps of firstly crushing aluminum-silicon overhaul residues to obtain crushed materials, then mixing the crushed materials with a manganese-rich source and aluminum oxide to supplement manganese lacking in the aluminum-silicon overhaul residues, wherein the aluminum oxide can adsorb hydrogen fluoride in the electrolytic process to play a role in heat preservation, can form good crust on an electrolyte, shields an electrolyte melt, reduces heat loss, effectively protects anode oxidation and reduces anode consumption; electrolyzing the prepared raw materials to obtain the aluminum-manganese alloy; in the process, the aluminum-silicon overhaul slag and the alumina are smoothly dissolved and diffused by adopting the raw materials, the proportioning relation of the raw materials and the adjustment of related parameters, and finally, the aluminum-manganese alloy with high purity and low impurity content is obtained. The invention not only utilizes the unused electrolysis method to prepare the aluminum-manganese alloy at the present stage, but also solves the problem of pollution of fluoride and cyanide in the overhaul slag solid waste in the aluminum electrolysis industry, and realizes the harmless treatment, the reduction treatment and the resource treatment of the waste lining of the aluminum electrolysis cell.
Drawings
FIG. 1 is a schematic diagram of a blanking process according to an embodiment of the present invention;
FIG. 2 is a schematic view of the preparation process of the aluminum-manganese alloy of the present invention.
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.
In view of the recycling problem of aluminum-silicon overhaul residues in the prior art, the application provides a preparation method of an aluminum-manganese alloy, the aluminum-manganese alloy prepared by an electrolytic method has high purity, low impurity content and high chemical stability, and on the other hand, an electrolytic tank in an aluminum electrolysis plant is used as an electrolytic reaction tank, so that excessive equipment capital investment is not needed, the electrolytic technology is mature, the pollution problem of fluoride and cyanide in overhaul residue solid waste in the aluminum electrolysis industry is solved, the harmless treatment, the reduction treatment and the resource treatment of waste and old linings of the aluminum electrolytic tank are realized, and the obtained aluminum-manganese alloy is a high-value product and has better feasibility and economical efficiency. Specifically, the preparation method of the aluminum-manganese alloy provided by the application comprises the following steps:
A) crushing the aluminum-silicon overhaul residues to obtain a crushed material, wherein the aluminum content in the crushed material is 15-20 wt%, and the iron content is less than or equal to 5 wt%;
B) mixing a manganese-rich source, aluminum oxide and the crushed materials, and then feeding the mixture into an electrolytic cell for electrolysis to obtain an aluminum-manganese alloy; the electrolyte superheat degree of the electrolysis is 9-13 ℃.
In the process of preparing the aluminum-manganese alloy, firstly, crushing aluminum-silicon overhaul residues to obtain crushed materials; in the process, the aluminum-silicon overhaul slag is aluminum-silicon solid waste in the aluminum electrolysis industry, which is well known to those skilled in the art, and can comprise materials such as light castable, ceramic fiber board, clay heat-insulating refractory brick, dry type impermeable material, high-aluminum refractory brick, high-strength castable, impermeable brick and the like. In order to guarantee the quick dissolution of ferro-silicon-aluminum overhaul sediment, guarantee the normal electrolysis of silicon, kibbling process specifically is:
firstly, feeding the aluminum-silicon overhaul slag into a jaw crusher for primary crushing, then feeding the crushed material into a two-in-one impact hammer crusher for crushing through a continuously operated belt conveyor, wherein the particle size of the material is less than or equal to 5mm, then feeding the crushed material into a vertical pulverizer, and sieving the crushed material to obtain the crushed material with the particle size of less than or equal to 0.15 mm.
The aluminum content in the crushed material is 15-20 wt%, and the iron content is less than or equal to 5 wt%. The elemental composition content of the aluminum-silicon overhaul slag is shown in table 1:
TABLE 1 elemental composition data sheet of alumino-siliceous overhaul slag
The applicant obtains that the Mn content in the aluminum-silicon overhaul slag is low through component analysis, and a proper amount of manganese-rich source needs to be added; the manganese-rich source adopts manganese-rich slag in the embodiment, wherein the manganese-rich slag contains 20-30 wt% of manganese, 3-3.5 wt% of iron and 0.01-0.05 wt% of phosphorus; the manganese-rich residue can also be replaced by manganese oxide, manganese roselle, manganese garnet or manganese olivine. The manganese-rich slag is obtained by adding insufficient carbon as a reducing agent into lean manganese ore which can not be directly used for smelting and has high iron content and high phosphorus content, and fully reducing iron and phosphorus in a lower furnace temperature and acid slag, so that manganese is remained in the slag to the maximum extent.
According to the invention, the crushed materials are mixed with alumina and a manganese-rich source, and then fed into an electrolytic cell for electrolytic reaction, so as to obtain the aluminum-manganese alloy; the blanking process of the raw materials related to the application is shown in figure 1, and the process of preparing the sendust is shown in figure 2. The alumina and the manganese-rich source are preferably added in the form of powder, and a small amount of iron, chromium, nickel and the like can be added for electrolytic reaction according to the requirements of other elements in the aluminum-manganese alloy; the aluminum oxide can adsorb hydrogen fluoride, can play a role in heat preservation, can form a good crust on the electrolyte, shields the electrolyte melt and reduces heat loss; effectively protects the anode from oxidation and reduces the consumption of the anode.
The chemical properties (purity) of alumina are the main factors affecting the quality of raw aluminum and also the technical and economic indicators of the aluminum electrolysis process, such as current efficiency and fluoride consumption, so the content of impurities in alumina must be reduced as much as possible. Sodium oxide is the main impurity in the alumina product, the increase of the content of sodium oxide in the alumina has great influence on the operation of the electrolytic cell, when the content of sodium in the electrolyte is increased, more alumina must be added to maintain the normal NaF/AlF3 ratio, the consumption of fluoride salt is increased, and the volume of the electrolyte in the electrolytic cell is increased; the sodium oxide in the aluminum oxide plays an important role in the chemical change of the electrolyte and the aspects of the material transmission and the process control of the electrolytic cell; in the aluminum electrolysis, sodium oxide can react with aluminum fluoride to generate sodium fluoride, so that the normal molecular ratio of the electrolyte is changed, and in order to maintain the normal composition of the electrolyte, a corresponding amount of aluminum fluoride must be supplemented. Oxide impurities (Fe2O3, SiO2, TiO2, etc.) contained in alumina, which are more electrically conductive than aluminum, are first precipitated on the cathode to deteriorate the quality of the original aluminum and affect the current efficiency. Therefore, the addition of pure alumina is required.
In the electrolytic process, the related raw materials comprise a manganese-rich source, aluminum oxide and a crushed material, wherein the content of the manganese-rich source is 10-20 wt%, the content of the crushed material is 5-50 wt%, and the balance is the aluminum oxide.
In the process of electrolysis, the mixture is added into the aluminum electrolysis cell, the dissolution speed of the mixture is slower than that of alumina, and the consumption of fluoride salt is increased, so that the parameters of the existing aluminum electrolysis cell need to be adjusted. The electrolyte adopted by electrolysis is cryolite-based molten salt, the main component of which is cryolite, and a small amount of magnesium fluoride, potassium fluoride, calcium fluoride, lithium fluoride, aluminum oxide and silicon dioxide; spodumene can also be added according to the requirement, the main component of the spodumene is lithium aluminosilicate, the component can recover silicon on one hand, and Li on the other hand can reduce the viscosity of electrolyte, and is beneficial to the dissolution and diffusion of overhaul residues. Specifically, the electrolytic electrolyte comprises 2.10-3.35 wt% of magnesium fluoride, 1.35-2.55 wt% of lithium fluoride, 3.00-5.45 wt% of calcium fluoride, 1.00-2.40 wt% of potassium fluoride, 1.00-3.30 wt% of alumina, 0.10-1.50 wt% of manganese dioxide and the balance of cryolite; in a specific embodiment, the electrolyte comprises 3.345-2.134 wt% of magnesium fluoride, 1.354-2.524 wt% of lithium fluoride, 3.046-5.423 wt% of calcium fluoride, 1.056-2.356 wt% of potassium fluoride, 1.031-3.261 wt% of alumina, 0.4-1.2 wt% of manganese dioxide and the balance cryolite; according to actual needs, the electrolyte also comprises 1.26-3.34 wt% of spodumene and 2.37-3.12 wt% of boride. The molecular ratio of the electrolyte cryolite-based molten salt, namely the molecular ratio of sodium fluoride to aluminum fluoride, is preferably 2.3-2.6: 1.
in the electrolysis process, boride can be added in the initial stage of electrolysis, a Ti-B-C protective layer can be formed on the cathode carbon block, the pressure drop is reduced, the service life of the cathode is prolonged, the aluminum-manganese alloy electrolytic cell is naturally formed, the cost is saved, the construction period is shortened, and the raw materials only need to be added with boride by utilizing Ti in overhaul residues and C of the cathode. The viscosity of the mixed material is increased along with the addition of the mixed material, and in order to ensure that the dissolved alumina and aluminum-silicon solid waste crushed aggregates can be smoothly dissolved and diffused, the superheat degree of the electrolyte is 9-13 ℃. When the content of the crushed materials is 5-20 wt%, the electrolysis temperature of electrolysis is 910-930 ℃, and when the content of the crushed materials is 21-50 wt%, the electrolysis temperature of electrolysis is 950-960 ℃; the electrolytic voltage is 3.8-4.6V, in the specific embodiment, the electrolytic voltage is 4.0-4.2V, so that the production of the Al-Si-Fe alloy by the electrolytic reaction can be carried out in a long-term stable state, and the current efficiency is 86-93%, so that the aluminum and the manganese have higher recovery efficiency.
The method for preparing the aluminum-manganese alloy by electrolysis by using the aluminum electrolytic cell as an electrolytic cell has the difficulties of reasonable proportioning of raw materials, reasonable feeding, reasonable control of electrolysis voltage and electrolysis temperature, smooth dissolution and diffusion of alumina and overhaul slag and adjustment of the electrolyte parameters of the conventional aluminum electrolytic cell.
Because the purity of the aluminum-silicon overhaul slag is not high as that of raw materials such as aluminum slag powder, silica sand and the like, when aluminum-silicon solid wastes are used as the raw materials for electrolyzing to produce the aluminum-manganese alloy, the carbon slag and furnace bottom sediment are increased compared with the pure aluminum electrolysis, the blanking amount can be manually controlled to increase the anode effect times, remove the carbon slag and reduce the furnace bottom sediment, because most of the anode effect is the material shortage effect, the blanking amount is reduced, the anode effect is generated, the furnace bottom sediment is consumed, and the recovery rate of Al and Mn is improved.
The method for preparing the aluminum-manganese alloy is a brand-new method for preparing the aluminum-manganese alloy, the aluminum-manganese alloy with more stable chemical property and higher purity is obtained by the novel method, and the aluminum-manganese alloy is prepared by utilizing overhaul slag solid waste which is generated by electrolytic aluminum industry and is harmful to the environment, so that the environmental problem of solid waste stockpiling is solved, the solid waste is recycled, and the direct economic value is brought.
For further understanding of the present invention, the following examples are provided to illustrate the preparation method of the aluminum manganese series of the present invention, and the scope of the present invention is not limited by the following examples.
Example 1
Crushing the aluminum-silicon solid waste in the waste tank lining to obtain a solid waste crushed material with the particle size of less than or equal to 0.15 mm; mixing the ground crushed material with alumina powder and manganese-rich slag powder according to a certain proportion to obtain a mixture; the content of aluminum in the crushed material is 16.2 wt%, the content of iron is 3.56 wt%, the content of silicon is 12.41 wt%, and the content of manganese in the manganese-rich slag is 25 wt%; the mass of the aluminum-silicon solid waste in the mixture is 5 wt% of the mass of the mixture, the mass of the manganese-rich slag is 10 wt% of the mass of the mixture, and the balance is aluminum oxide;
adding the mixture into an electrolytic cell for electrolysis, wherein the working voltage of the electrolytic cell is 4.018V, the current efficiency is 93.3%, the electrolysis temperature is 910 ℃, and the electrolyte comprises: 3.345 weight percent of magnesium fluoride, 2.524 weight percent of lithium fluoride, 5.423 weight percent of calcium fluoride, 2.356 weight percent of potassium fluoride, 3.261 weight percent of alumina, 1.48 weight percent of manganese dioxide, 1.26 weight percent of spodumene, 2.37 weight percent of boride and the balance of cryolite; the molecular ratio of the cryolite-based molten salt, namely the molecular ratio of sodium fluoride to aluminum fluoride, is 2.3, and the superheat degree of the electrolyte is 11 ℃; after electrolysis, the chemical components (mass percent) are as follows: al (95.6%), Mn (3.6%), Si (0.75%) and the rest is impurity Al-Mn-Si alloy product. The recovery of aluminum was 81% and the recovery of manganese was 92%.
Example 2
Crushing the aluminum-silicon solid waste in the waste tank lining to obtain a solid waste crushed material with the particle size of less than or equal to 0.15 mm; mixing the ground crushed material with alumina powder and manganese-rich slag powder according to a certain proportion to obtain a mixture; the content of aluminum in the crushed material is 16.2 wt%, the content of iron is 3.56 wt%, the content of silicon is 12.41 wt%, and the content of manganese in the manganese-rich slag is 25 wt%; the mass of the aluminum-silicon solid waste in the mixture is 20 wt% of the mass of the mixture, the mass of the manganese-rich slag is 10 wt% of the mass of the mixture, and the balance is aluminum oxide;
adding the mixture into an electrolytic cell for electrolysis, wherein the working voltage of the electrolytic cell is 4.095V, the electrolysis temperature is 922 ℃, the current efficiency is 90.2%, and the electrolyte comprises: 2.956 wt% of magnesium fluoride, 1.986 wt% of lithium fluoride, 4.623 wt% of calcium fluoride, 1.946 wt% of potassium fluoride, 2.95 wt% of alumina, 1.1 wt% of manganese dioxide, 1.57 wt% of spodumene, 2.58 wt% of boride and the balance of cryolite; the molecular ratio of the cryolite-based molten salt, namely the molecular ratio of sodium fluoride to aluminum fluoride, is 2.4, and the superheat degree of the electrolyte is 11 ℃; the chemical components (mass percent) obtained by electrolysis are as follows: al (94.7%), Mn (4%), Fe (1%), and the balance of impurities. The recovery of aluminum was 78.2% and the recovery of manganese was 85.4%.
Example 3
Crushing the aluminum-silicon solid waste in the waste tank lining to obtain a solid waste crushed material with the particle size of less than or equal to 0.15 mm; mixing the ground crushed material with alumina powder, manganese-rich slag powder and chromium-containing waste slag (the chromium content is 85%) according to a certain proportion to obtain a mixture; the content of aluminum in the crushed material is 16.2 wt%, the content of iron is 3.56 wt%, the content of silicon is 12.41 wt%, and the content of manganese in the manganese-rich slag is 25 wt%; the mass of the aluminum-silicon solid waste in the mixture is 30 wt% of the mass of the mixture, the mass of the manganese-rich slag is 20 wt% of the mass of the mixture, the mass of the chromium-containing waste slag (containing Cr85 wt%) is 5 wt% of the mass of the mixture, and the balance is alumina;
adding the mixture into an electrolytic cell for electrolysis, wherein the working voltage of the electrolytic cell is 4.14V, the electrolysis temperature is 952 ℃, the current efficiency is 87.2 percent, and the electrolyte comprises: 2.025 weight percent of magnesium fluoride, 1.045 weight percent of lithium fluoride, 2.976 weight percent of calcium fluoride, 1.053 weight percent of potassium fluoride, 1.135 weight percent of aluminum oxide, 0.71 weight percent of manganese dioxide, 1.96 weight percent of spodumene, 2.73 weight percent of boride and the balance of cryolite, wherein the molecular ratio of the cryolite-based molten salt, namely the molecular ratio of sodium fluoride to aluminum fluoride, is 2.5, and the superheat degree of an electrolyte is 9 ℃; the chemical components (mass percent) obtained by electrolysis are as follows: al (87.7%), Mn (10.2%), Cr (1.9%) and the rest is impurity Al-Mn-Cr alloy product. The recovery rate of aluminum was 75% and the recovery rate of manganese was 80.1%.
Example 4
Crushing the aluminum-silicon solid waste in the waste tank lining to obtain a solid waste crushed material with the particle size of less than or equal to 0.15 mm; mixing the ground crushed material with alumina powder, manganese-rich slag powder and waste nickel powder (about 99% of the waste nickel raw material is nickel-containing waste materials in various forms from stainless steel, super heat-resistant alloy to storage batteries) according to a certain proportion to obtain a mixture; the content of aluminum in the crushed material is 16.2 wt%, the content of iron is 3.56 wt%, the content of silicon is 12.41 wt%, and the content of manganese in the manganese-rich slag is 25 wt%; the mass of the aluminum-silicon solid waste in the mixture is 50 wt% of the mass of the mixture, the mass of the manganese-rich slag is 20 wt% of the mass of the mixture, the mass of the waste nickel is 5 wt% of the mass of the mixture, and the balance is aluminum oxide;
the mixture is added into an electrolytic cell for electrolysis, the working voltage of the electrolytic cell is 4.2V, the electrolysis temperature is 958 ℃, the current efficiency is 85.4 percent, and the electrolyte comprises: 2.134 wt% of magnesium fluoride, 1.354 wt% of lithium fluoride, 3.046 wt% of calcium fluoride, 1.056 wt% of potassium fluoride, 1.031 wt% of aluminum oxide, 0.11 wt% of manganese dioxide and the balance of cryolite, wherein the molecular ratio of the cryolite-based molten salt, namely the molecular ratio of sodium fluoride to aluminum fluoride, is 2.6, and the superheat degree of the electrolyte is 9 ℃; the chemical components (mass percent) obtained by electrolysis are as follows: al (81.8%), Mn (13.8%), Ni (4.3%), and the balance of impurities. The recovery of aluminum was 72% and the recovery of manganese was 78%.
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 (5)
1. A preparation method of an aluminum-manganese alloy comprises the following steps:
A) crushing the aluminum-silicon overhaul residues to obtain a crushed material, wherein the aluminum content in the crushed material is 15-20 wt%, and the iron content is less than or equal to 5 wt%;
B) mixing manganese-rich slag, aluminum oxide and the crushed materials, and then feeding the mixture into an electrolytic cell for electrolysis to obtain an aluminum-manganese alloy; the electrolyte superheat degree of the electrolysis is 9-13 ℃;
the manganese-rich slag contains 20-30 wt% of manganese, 3-3.5 wt% of iron and 0.01-0.05 wt% of phosphorus;
the electrolyte for electrolysis is cryolite-based molten salt, and comprises 2.10-3.35 wt% of magnesium fluoride, 1.35-2.55 wt% of lithium fluoride, 3.00-5.45 wt% of calcium fluoride, 1.00-2.40 wt% of potassium fluoride, 1.00-3.30 wt% of aluminum oxide, 0.10-1.50 wt% of manganese dioxide and the balance cryolite, and further comprises 1.26-3.34 wt% of spodumene and 2.37-3.12 wt% of boride;
the manganese-rich source content in a mixed material obtained by mixing the manganese-rich source, the alumina and the crushed material is 10-20 wt%, the crushed material content is 5-50 wt%, and the balance is the alumina.
2. The method according to claim 1, wherein the cryolite-based molten salt has a molecular ratio of sodium fluoride to aluminum fluoride of (2.3 to 2.6): 1.
3. the preparation method according to claim 1, wherein the pulverization in step a) is specifically carried out by:
feeding the aluminum-silicon overhaul slag into a jaw crusher for primary crushing, feeding the obtained initial material into a reaction hammer crusher for secondary crushing, feeding the obtained material into a vertical pulverizer, and sieving to obtain a crushed material;
the grain diameter of the materials after the re-crushing is less than or equal to 5mm, and the grain diameter of the crushed materials is less than or equal to 0.15 mm.
4. The method according to claim 1, wherein the electrolysis temperature is 910 to 930 ℃ when the content of the pulverized material is 5 to 20 wt%, and the electrolysis temperature is 950 to 960 ℃ when the content of the pulverized material is 21 to 50 wt%; the electrolytic voltage of the electrolysis is 4.0-4.2V, and the current efficiency is 85-94%.
5. The method according to claim 1, wherein the aluminum-manganese alloy contains 80 to 95 wt% of aluminum and 3 to 14 wt% of manganese.
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| US3951764A (en) * | 1974-02-28 | 1976-04-20 | Kaiser Aluminum & Chemical Corporation | Aluminum-manganese alloy |
| SU1068546A1 (en) * | 1982-06-23 | 1984-01-23 | Всесоюзный Научно-Исследовательский И Проектный Институт Алюминиевой,Магниевой И Электродной Промышленности | Method for preparing aluminium-silicon-manganese master alloy in aluminium electrolytic cell |
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