CN109898029B - Preparation method of low-cost iron-cobalt alloy - Google Patents
Preparation method of low-cost iron-cobalt alloy Download PDFInfo
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- CN109898029B CN109898029B CN201910357662.7A CN201910357662A CN109898029B CN 109898029 B CN109898029 B CN 109898029B CN 201910357662 A CN201910357662 A CN 201910357662A CN 109898029 B CN109898029 B CN 109898029B
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Abstract
The invention relates to a preparation method of a low-cost iron-cobalt alloy, belonging to the technical field of soft magnetic material manufacture and comprising the following steps: taking high cobalt slag, red mud and coke powder as raw materials; coarsely crushing the high cobalt slag; ball-milling the coarsely crushed high cobalt slag, red mud and coke powder respectively, and sieving; mixing the sieved raw materials in a mixer to obtain a mixture; adding sodium carboxymethylcellulose aqueous solution into the mixture, pelletizing and drying; and (4) carrying out carbon thermal reduction smelting, and carrying out magnetic separation on the obtained reduction product to obtain the iron-cobalt alloy. The invention takes Bayer process red mud and high cobalt slag as main raw materials, produces the soft magnetic alloy with extremely high saturation induction intensity, is suitable for various complex, miniaturized and multifunctional high-power soft magnetic devices, and has the characteristics of simple process and low cost.
Description
Technical Field
The invention belongs to the technical field of soft magnetic material manufacturing, and particularly relates to a preparation method of a low-cost iron-cobalt alloy.
Background
The global alumina yield exceeds one hundred million tons, and the annual alumina yield in China reaches about 5000 million tons. The red mud is used as solid waste slag discharged in the process of extracting aluminum oxide in the aluminum production industry, and the yield of the red mud is continuously increased. About 1-1.2 tons of red mud are produced per 1 ton of alumina produced. The red mud not only has the characteristics of large content of combined chemical alkali and difficult removal, but also contains a large amount of Fe2O3，A12O3And CaO and other effective components, which are not properly treated and disposed, not only cause great harm to the environment and human bodies, but also cause waste of the effective components in the red mud. The cobalt ore resources in China are still relatively scarce and only account for about 1 percent of the total amount of the cobalt ores in the world. The method for extracting cobalt by smelting the high-cobalt slag and the waste containing cobalt again is an effective way for increasing cobalt resources. The high cobalt slag produced in the purification process of wet zinc smelting is a cobalt-containing material produced in the process of comprehensive utilization of nickel cobalt slag, and the high cobalt slag produced by the enterprises of wet zinc smelting in China is nearly 5000 tons every year, and the high cobalt slag accumulated in the past year is more than 5 ten thousand tons, so that heavy metal pollution is easily caused to soil and water due to improper stockpiling. The industrial waste is reasonably utilized, and the best efficiency of secondary resources is exerted to the greatest extent. Processing the waste into high value-added products, so as to do the pair ringEnvironmental protection, resource regeneration and reuse are very beneficial.
With the continuous advance of aerospace industry and deep sea exploration steps in China, magnetic materials are required to have high magnetic performance and high stability. The iron-cobalt alloy is a soft magnetic alloy with extremely high saturation induction strength, and the cobalt content is within the range of 27-50%. The organization structure is a single-phase solid solution of body-centered cubic lattice. Has higher Curie temperature, can work under the condition of higher temperature that other soft magnetic materials are completely demagnetized and failed, and has higher magnetic stability. Because the price is expensive, the material is mainly used in the high-tech fields with certain requirements on the lightening of power devices, such as the aerospace field, and is difficult to be widely popularized and applied.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a low-cost iron-cobalt alloy preparation method, which uses metallurgical industrial waste as a main raw material, and has low production cost and high magnetic stability.
In order to achieve the purpose, the invention adopts the specific scheme that:
a preparation method of a low-cost iron-cobalt alloy comprises the following steps:
step one, respectively taking high cobalt slag, red mud and coke powder as raw materials for later use;
step two, crushing the high cobalt slag obtained in the step one into particles with the particle size of less than 10 mm;
step three, ball-milling the high-cobalt slag particles crushed in the step two and the Bayer process red mud and coke powder obtained in the step one for 8-10 hours by using a ball mill respectively, and sieving the ball-milled particles by using a 200-mesh sieve;
step four, putting the raw materials sieved in the step three into a three-dimensional mixer to be mixed for 10 hours to obtain a mixture for later use;
adding sodium carboxymethylcellulose aqueous solution into the mixture, pelletizing by a pellet mill, wherein the particle size of the green pellets is 6-20mm, and drying for 4-6 h in a blast drying oven at 70-80 ℃ to obtain dried green pellets;
step six, sending the dried green pellets obtained in the step five into a vacuum arc furnace for high-temperature direct carbon heatingReduction smelting with vacuum degree of 102~103Pa and argon are used as working gas, smelting is carried out for 1-1.5 h at 1400-1450 ℃, then magnetic separation is carried out by a magnetic separation tube at 0.05T, and the iron-cobalt alloy and slag are separated to obtain the iron-cobalt alloy.
As a further optimization of the scheme, the high cobalt slag is produced by purifying and removing cobalt in zinc hydrometallurgy; the red mud is Bayer process red mud. Furthermore, the dosage of each raw material is as follows according to the weight percentage: 30-40% of high cobalt slag, 40-50% of Bayer process red mud and 20-30% of coke powder.
As a further optimization of the scheme, the mass volume percentage concentration of the sodium carboxymethyl cellulose aqueous solution is 1.25%. Furthermore, 1 to 1.5 mass percent of sodium carboxymethylcellulose aqueous solution is added into the mixture.
The principle of the invention is as follows: the Bayer process red mud comprises the following main components: fe2O3(25~30%)、A12O3、CaO、SiO2、TiO2、Na2O, the high cobalt slag produced by purifying and removing cobalt by zinc hydrometallurgy mainly comprises the following components: ZnO, Co2O3(23~28%)、MnO2、Fe2O3(0.2-0.3%) under a vacuum of 10%2~103Pa, 1400-1450 ℃ and Fe2O3、Co2O3Reduced to liquid metal by coke powder, and A12O3、CaO、SiO2、TiO2、Na2O、ZnO、MnO2The cobalt-free soft magnetic material can not be reduced to slag, and the proportion of the cobalt in the soft magnetic material finished product can be controlled to be 27-50% by optimizing the proportion of the Bayer process red mud and the high-cobalt slag.
Advantageous effects
1. The soft magnetic material of the invention takes Bayer process red mud and high cobalt slag as main raw materials, has low cost, saves energy, is suitable for industrial production, and has obvious promotion effect on environmental protection and promotion of preparation of new energy key materials.
2. According to the invention, the carbothermic reduction process is controlled, the red mud iron and the cobalt in the high-cobalt slag are selectively reduced to form a material which is directly applied to a terminal product, and the CaO in the red mud can improve the alkalinity of the slag, so that the slag and the alloy are better separated, and the low-carbon production of the soft magnetic material is realized.
3. The saturation magnetic flux density of the soft magnetic material prepared by the invention can reach 2.12-2.22T, the maximum working temperature can reach Curie temperature of 950-990 ℃, and the material also has higher yield strength, so the soft magnetic material is widely applied to manufacturing aviation electric appliances with light weight, small volume and high working temperature.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
A preparation method of a low-cost iron-cobalt alloy comprises the following specific steps:
(1) respectively taking 30% of high cobalt slag, 45% of Bayer process red mud and 25% of coke powder according to the weight percentage for later use;
(2) coarsely crushing the high cobalt slag into particles with the particle size of less than 10 mm;
(3) respectively ball-milling the coarsely crushed high-cobalt slag particles, Bayer process red mud and coke powder for 8 hours by using a ball mill, and sieving by using a 200-mesh sieve after ball milling;
(4) putting the sieved raw materials into a three-dimensional mixer to be mixed for 10 hours to obtain a mixture for later use;
(5) adding 1.25 vol% sodium carboxymethylcellulose aqueous solution into the mixture, pelletizing by a pellet mill, wherein the average particle size of green pellets is 10mm, and drying for 4 hours in a forced air drying oven at 70 ℃ to obtain dried green pellets;
(6) sending the dried green pellets into a vacuum arc furnace for high-temperature direct carbon thermal reduction smelting with the vacuum degree of 102Pa and argon are used as working gas, smelting is carried out for 1.2h at 1450 ℃, the obtained reduction product is subjected to magnetic separation by a magnetic separation tube at 0.05T, and the iron-cobalt alloy is separated from slag to obtain the iron-cobalt alloy.
The saturation magnetic flux density of the soft magnetic material prepared at this time can reach 2.15T, and the maximum working temperature can reach the Curie temperature of 960 DEG C
Example 2
A preparation method of a low-cost iron-cobalt alloy comprises the following specific steps:
(1) respectively taking 40% of high cobalt slag, 40% of Bayer process red mud and 20% of coke powder according to the weight percentage for later use;
(2) coarsely crushing the high cobalt slag into particles with the particle size of less than 10 mm;
(3) respectively ball-milling the coarsely crushed high-cobalt slag particles, Bayer process red mud and coke powder for 10 hours by using a ball mill, and sieving by using a 200-mesh sieve after ball milling;
(4) putting the sieved raw materials into a three-dimensional mixer to be mixed for 10 hours to obtain a mixture for later use;
(5) adding 1.25 vol% sodium carboxymethylcellulose aqueous solution into the mixture, pelletizing by a pellet mill to obtain green pellets with the average particle size of 15mm, and drying in a forced air drying oven at 80 ℃ for 6h to obtain dried green pellets;
(6) sending the dried green pellets into a vacuum arc furnace for high-temperature direct carbon thermal reduction smelting with the vacuum degree of 103Pa and argon gas are used as working gas, smelting is carried out for 1h at 1420 ℃, the obtained reduction product is subjected to magnetic separation by a magnetic separation tube at 0.05T, and the iron-cobalt alloy is separated from slag to obtain the iron-cobalt alloy.
The saturation magnetic flux density of the soft magnetic material prepared at this time reaches 2.2T, and the maximum working temperature can reach the Curie temperature of 970 DEG C
Example 3
A preparation method of a low-cost iron-cobalt alloy comprises the following specific steps:
(1) respectively taking 35% of high cobalt slag, 42% of Bayer process red mud and 23% of coke powder according to the weight percentage for later use;
(2) coarsely crushing the high cobalt slag into particles with the particle size of less than 10 mm;
(3) respectively ball-milling the coarsely crushed high-cobalt slag particles, Bayer process red mud and coke powder for 8.5 hours by using a ball mill, and sieving by using a 200-mesh sieve after ball milling;
(4) putting the sieved raw materials into a three-dimensional mixer to be mixed for 10 hours to obtain a mixture for later use;
(5) adding 1.25 vol% sodium carboxymethylcellulose aqueous solution into the mixture, pelletizing by a pellet mill, drying at 72 ℃ in a forced air drying oven for 4.5 hours to obtain dried green pellets, wherein the average particle size of the green pellets is 18 mm;
(6) sending the dried green pellets into a vacuum arc furnace for high-temperature direct carbon thermal reduction smelting with the vacuum degree of 102Pa and argon as working gas, smelting for 1.4h at 1440 ℃, magnetically separating the obtained reduction product by a magnetic separation tube at 0.05T, and separating the iron-cobalt alloy from the slag to obtain the iron-cobalt alloy.
The saturation magnetic flux density of the soft magnetic material prepared at this time reaches 2.19T, and the maximum working temperature can reach the Curie temperature of 965 DEG C
It should be noted that the above-mentioned embodiments illustrate rather than limit the scope of the invention, which is defined by the appended claims. It will be apparent to those skilled in the art that certain insubstantial modifications and adaptations of the present invention can be made without departing from the spirit and scope of the invention.
Claims (4)
1. A preparation method of low-cost iron-cobalt alloy is characterized by comprising the following steps: the method comprises the following steps:
step one, respectively taking high cobalt slag, Bayer process red mud and coke powder as raw materials for later use;
step two, crushing the high cobalt slag obtained in the step one into particles with the particle size of less than 10 mm;
step three, ball-milling the high-cobalt slag particles crushed in the step two and the Bayer process red mud and coke powder obtained in the step one for 8-10 hours by using a ball mill respectively, and sieving the ball-milled particles by using a 200-mesh sieve;
step four, putting the raw materials sieved in the step three into a three-dimensional mixer to be mixed for 10 hours to obtain a mixture for later use;
adding sodium carboxymethylcellulose aqueous solution into the mixture, pelletizing by a pellet mill, wherein the particle size of the green pellets is 6-20mm, and drying for 4-6 h in a blast drying oven at 70-80 ℃ to obtain dried green pellets;
step six, the dried green pellets obtained in the step five are sent to a vacuum arc furnace for high-temperature direct carbon thermal reduction smelting, and the vacuum degree is 102~103Pa and argon are used as working gas, smelting is carried out for 1-1.5 h at 1400-1450 ℃, and thenAnd (4) carrying out magnetic separation by using a magnetic separation tube at 0.05T to separate the iron-cobalt alloy from the slag to obtain the iron-cobalt alloy.
2. The method for preparing the low-cost iron-cobalt alloy according to claim 1, wherein the method comprises the following steps: the high cobalt slag is produced by purifying and removing cobalt in zinc hydrometallurgy.
3. The method for preparing the low-cost iron-cobalt alloy according to claim 2, wherein the method comprises the following steps: according to the weight percentage, the dosage of each raw material is respectively as follows: 30-40% of high cobalt slag, 40-50% of Bayer process red mud and 20-30% of coke powder.
4. The method for preparing the low-cost iron-cobalt alloy according to claim 1, wherein the method comprises the following steps: the mass volume percentage concentration of the sodium carboxymethylcellulose aqueous solution is 1.25%.
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