Method for preparing multi-element alloy by powder spraying technology
阅读说明：本技术 一种利用喷粉技术制备多元合金的方法 (Method for preparing multi-element alloy by powder spraying technology ) 是由 魏创林 魏伟 王凯 魏佳新 魏波 李健仁 乔泓博 周廷 寇娟 赵红波 岳静 于 2020-11-25 设计创作，主要内容包括：本发明涉及一种利用喷粉技术制备多元合金的方法,通过向精炼炉内加入孔隙状多元合金复合烧结料、块状除尘粉、工业废渣、兰炭,直至炉内原料全部熔融后采用喷粉的方式通过插入到炉内的金属输料管道向合金溶液中加入除尘粉,除尘粉全部熔炼到金属溶液后,对合金液采样化验,与设计的合金成分比较后,进一步根据元素含量要求加入相应质量的除尘粉、工业废渣等物质,直至熔炼的多元合金化学成分达到设计的合金成分为止。本发明通过喷粉的方式制备多元合金,充分利用了冶金行业回收的除尘粉以及含金属元素的工业废渣,同时又发挥了人工造渣剂的作用,使得合金溶液液面上方形成较厚的渣层,在喷粉过程中抵挡金属液的翻滚和飞溅。(The invention relates to a method for preparing multi-element alloy by using powder spraying technology, which comprises the steps of adding porous multi-element alloy composite sintering material, blocky dedusting powder, industrial waste residue and semi coke into a refining furnace, adding the dedusting powder into an alloy solution through a metal conveying pipeline inserted into the furnace in a powder spraying mode until raw materials in the furnace are completely molten, sampling and testing the alloy solution after the dedusting powder is completely molten into the metal solution, comparing with designed alloy components, and further adding the dedusting powder, the industrial waste residue and other substances with corresponding mass according to element content requirements until the chemical components of the molten multi-element alloy reach the designed alloy components. The multi-component alloy is prepared in a powder spraying manner, dust removal powder recovered in the metallurgical industry and industrial waste residues containing metal elements are fully utilized, and meanwhile, the effect of an artificial slagging agent is exerted, so that a thick slag layer is formed above the liquid level of an alloy solution, and the metal liquid is prevented from rolling and splashing in the powder spraying process.)
1. A method for preparing a multi-element alloy by using a powder spraying technology is characterized by comprising the following specific preparation steps:
step 1: designing alloy components, and adding the following raw materials into a refining furnace: the porous multi-element alloy composite sintering material, the blocky dedusting powder, the industrial waste residue and the semi-coke, wherein the adding amount of the porous multi-element alloy composite sintering material is not less than 60 percent of the total adding mass of the porous multi-element alloy composite sintering material, the blocky dedusting powder and the industrial waste residue, and the adding amount and the proportion of the raw materials meet the requirement that a slag layer with the thickness of not less than 10cm can be formed on the surface of an alloy solution after melting,
controlling the temperature in the furnace to be 1500-1800 ℃ until the raw materials in the furnace are completely melted, wherein the industrial waste residue comprises one or a mixture of more of silicon slag, barium slag and calcium slag;
step 2: adding dust removal powder into the alloy solution in the step 1 through a metal delivery pipeline inserted into the alloy solution in the furnace in a powder spraying manner, wherein the adding amount of the dust removal powder is 50% of the mass of the alloy raw material added in the step 1 at most;
and step 3: and (3) sampling and testing the alloy liquid, comparing the alloy liquid with the alloy components designed in the step (1), and then adding one or a mixture of more of dust removal powder, silicon slag, barium slag and calcium slag with corresponding mass according to the element content requirement until the chemical components of the smelted multi-element alloy reach the alloy components designed in the step (1).
2. The method for preparing the multi-component alloy by the powder spraying technology as claimed in claim 1, wherein the raw materials are added in the step 1 in such amounts and proportions that a slag layer with the thickness of 10 cm-20 cm can be formed on the surface of the alloy solution after melting.
3. A method for making a multi-component alloy by powder spraying according to claim 1, wherein the metal delivery pipe in step 2 is inserted into the alloy solution at a height of at least 20cm from the alloy solution surface.
4. A method for preparing multi-element alloy by powder spraying technology according to claim 1 or 3, wherein the number of the metal conveying pipes in the step 2 is at least 1, and the total number of the conveying pipes is 50kg/min to 70 kg/min.
5. The method for preparing the multi-component alloy by the powder spraying technology according to claim 4, wherein the dust removal powder is conveyed into the refining furnace through a gas-solid two-phase mixing pipeline, and the conveying pressure is 2MPa to 8 MPa.
6. A method for preparing multi-element alloy by powder spraying technology according to claim 1 or 5, characterized in that the porous multi-element alloy composite sintering material contains Si, Ba, Fe, Ca and Al metal elements.
7. The method for preparing multi-component alloy by powder spraying technology according to claim 1 or 5, wherein the block-shaped dust removal powder is formed by briquetting and sintering dust removal powder, the dust removal powder is micro silicon powder collected by a ferrosilicon smelting dust removal system and dust removal powder collected in a ferroalloy factory smelting process, and the chemical composition and content of the dust removal powder are 60-75% of SiO2、2％～10％BaO、1％～3％CaO、1％～5％Al2O3The balance being ash.
8. The method for preparing the multi-component alloy by the powder spraying technology according to the claim 1 or 5, wherein the silicon slag comprises the following components in percentage by weight: 60% -75% of SiO21 to 4 percent of Al2O3, 1 to 3 percent of CaO, 1 to 8 percent of BaO and the balance of ash and unreduced silica; the barium residue comprises the following components in percentage by weight: 30 to 50 percent of SiO2、10％～40％BaO、2％～％20％CaO、1％～5％Al2O3The balance of the catalyst is ash and unreduced silicobarite; the calcium slag comprises the following components: 20 to 35 percent of SiO2、55％～70％CaO、1％～6％Al2O3The balance being ash.
9. The method for preparing the multi-component alloy by the powder spraying technology according to the claim 1 or 5, wherein the porous multi-component alloy composite sintering material is prepared by sintering hill-stone, industrial waste residue, dust removal powder, coal gangue and fly ash.
Technical Field
The invention belongs to a preparation method of a multi-component alloy, and particularly relates to a method for realizing production of the multi-component alloy by utilizing dusting powder and industrial waste residue in a resource utilization mode through a dusting technology.
Background
In the prior art, when a refining furnace is used for smelting a multi-element alloy, because energy is provided by a high-voltage electric arc formed between an electrode and a conductive raw material, oxidation-reduction reaction occurs in the whole smelting process, and the air permeability in the furnace is required to be high, a large amount of powder raw materials cannot be added at one time during initial material distribution in the refining furnace and charging in the process, and the furnace is ignited and extinguished. In addition, because oxidation-reduction reaction is continuously generated among various substances and elements in the smelting process, too many powder raw materials are added at one time or too many powder raw materials are continuously added, the powder raw materials can form rolling floating on the slag in the molten metal, the molten metal can be taken out of the slag in the rolling process to cause splashing of the molten metal, and a furnace cover is broken down by electric arc, so that the powder spraying technology is not adopted for preparing the multi-element alloy products of the ferroalloy in the prior art.
Disclosure of Invention
The invention provides a preparation method of a multi-component alloy, which aims to solve the technical problems that when too much powder raw material is added at one time or too much powder raw material is continuously added in the ferroalloy industry, the gas permeability in a furnace is poor, and the furnace is easy to extinguish, and when powder metal, powder alloy or other powder raw material is added by adopting a powder spraying technology, the furnace cover is easy to be broken down by electric arc, and the like, and the preparation method of the multi-component alloy comprises the following specific steps:
step 1: designing alloy components, and adding the following raw materials into a refining furnace: the method comprises the following steps of preparing porous multi-element alloy composite sintering materials, blocky dust removal powder, industrial waste residues and semi-coke, wherein the adding amount of the porous multi-element alloy composite sintering materials is not less than 60% of the total adding amount of the porous multi-element alloy composite sintering materials, the blocky dust removal powder and the industrial waste residues, a slag layer with the thickness of not less than 10cm can be formed on the surface of an alloy solution after the raw materials are added in the materials in a melting mode, the temperature in a furnace is controlled to be 1500-1800 ℃ until the raw materials in the furnace are completely melted, and the industrial waste residues comprise one or a mixture of silicon residues, barium residues and calcium residues;
step 2: adding dust removal powder into the alloy solution in the step 1 through a metal delivery pipeline inserted into the alloy solution in the furnace in a powder spraying manner, wherein the adding amount of the dust removal powder is 50% of the mass of the alloy raw material added in the step 1 at most;
and step 3: and (3) sampling and testing the alloy liquid, comparing the alloy liquid with the alloy components designed in the step (1), and then adding one or a mixture of more of dust removal powder, silicon slag, barium slag and calcium slag with corresponding mass according to the element content requirement until the chemical components of the smelted multi-element alloy reach the alloy components designed in the step (1).
And after the tested components of the multi-element alloy are qualified, tapping and casting to form a multi-element alloy ingot, and crushing the multi-element alloy ingot into multi-element alloy particles or powder with different sizes according to the specification requirements of the order.
Preferably, the amount and the proportion of the raw materials added in the step 1 are such that a slag layer with the thickness of 10 cm-20 cm can be formed on the surface of the alloy solution after melting.
Preferably, the metal delivery pipe in step 2 is inserted into the alloy solution at a position which is at least 20cm away from the alloy liquid level.
Further, the number of the metal conveying pipes in the step 2 is at least 1, preferably 1, and the total amount of the conveying pipes is 50 kg/min-70 kg/min for spraying dust removal powder into the alloy liquid.
Further, the dust removal powder is conveyed into the refining furnace through a gas-solid two-phase mixed pipeline, and the conveying pressure is 2-8 Mpa.
Furthermore, the porous multi-element alloy composite sintering material contains various metal elements such as Si, Ba, Ca, Fe, Al and the like.
Preferably, the block-shaped dust removal powder is formed by briquetting and sintering dust removal powder, the dust removal powder is micro silicon powder collected by a ferrosilicon smelting dust removal system and dust removal powder collected in a ferroalloy factory smelting process, and the chemical components and the content of the chemical components are 60-75% of SiO2、2％～10％BaO、1％～3％CaO、1％～5％Al2O3The balance being ash.
Further, the silicon slag comprises the following components in percentage by weight: 60% -75% of SiO2、1％～4％Al2O31 to 3 percent of CaO, 1 to 8 percent of BaO, and the balance of ash and unreduced silica; the barium residue comprises the following components in percentage by weight: 30 to 50 percent of SiO2、10％～40％BaO、2％～％20％CaO、1％～5％Al2O3The balance of ash and unreduced silicobarite; the calcium slag comprises the following components: 20 to 35 percent of SiO2、55％～70％CaO、1％～6％Al2O3The balance being ash.
Further, the porous multi-element alloy composite sintering material is prepared by sintering mountain leather, industrial waste residues, dust removing powder, coal gangue and fly ash.
The invention has the following beneficial technical effects:
1. in the preparation method of the multi-element alloy, in the step 1, the blocky dedusting powder and the industrial waste residues are added into the raw materials, the dedusting powder recycled in the metallurgical industry and the industrial waste residues containing metal elements are fully recycled, the raw materials are added into the refining furnace and play the role of an artificial slag former, so that a slag layer with the thickness of not less than 10cm is formed above the liquid level of the alloy solution after the alloy raw materials are molten, and the slag layer can be ensured to be enough to resist the rolling and splashing of molten metal when the powder spraying is carried out in the step 2, so that the molten metal can not be splashed above the slag layer.
2. In the preparation method of the multi-element alloy, when the powder spraying in the step 2 is carried out, the metal delivery pipe is preferably inserted into the position at least 20cm away from the alloy liquid level, so that the kinetic energy of metal liquid splashing caused by redox reaction of powder substances is reduced and weakened again, and the rolling phenomenon is isolated below a slag layer.
3. In the preparation method of the multi-element alloy, when the powder spraying in the step 2 is implemented, the number of the metal conveying pipes in the step 2 can be multiple, the total flow of each conveying pipe is 50 kg/min-70 kg/min, the dust removal powder is sprayed into the alloy liquid, the amount of the powder entering the metal liquid in unit time is controlled, and the activity of the powder in the metal liquid in the oxidation-reduction reaction can be effectively slowed down.
4. In the preparation method of the multi-element alloy, when the powder spraying in the step 2 is carried out, the pressure in the material conveying pipe is strictly controlled to be between 2Mpa and 8Mpa, so that the dust removing powder can be ensured to be smoothly blown into the furnace, and the rolling and splashing of molten metal due to the too large assistance of the pressure can be avoided.
5. In the preparation method of the multi-element alloy, the dust removal powder is directly blown into the molten metal in the step 2 by adopting a powder spraying technology, and compared with smelting after sintering of a pressed block, the dust removal powder is instantly melted under the high-temperature action of the molten metal in a powder blowing mode, so that the metal elements are reduced to the maximum extent, and the formation of a slag layer is reduced to the maximum extent.
Detailed Description
The method for preparing the multi-element alloy by using the powder spraying technology comprises the following preparation implementation steps:
step 1: designing alloy components, wherein the alloy design components in the specific embodiment are shown in a table 1, and after the alloy components are designed, adding the following raw materials into a refining furnace: the porous multi-element alloy composite sintering material, the blocky dedusting powder, the industrial waste residue and the semi-coke are added, wherein the adding amount of the porous multi-element alloy composite sintering material is not less than 60 percent of the total adding amount of the porous multi-element alloy composite sintering material, the blocky dedusting powder and the industrial waste residue, and the adding amount and the proportion of each raw material meet the requirement that a slag layer with the thickness of not less than 10cm can be formed on the surface of an alloy solution after melting, and the adding amount of the raw materials in the specific embodiment is shown in table 2;
in the embodiment, the amount and the proportion of the raw materials added in the step 1 meet the requirement that a slag layer with the thickness of 10-20 cm can be formed on the surface of the alloy solution after melting;
controlling the temperature in the furnace to be 1500-1800 ℃ until the raw materials in the furnace are completely melted, and forming a thicker slag layer above the liquid level of the alloy solution after the raw materials in the furnace are completely melted, wherein the thickness of the formed slag layer is shown in Table 2 in the specific embodiment;
in the embodiment of the invention, the porous multi-element alloy composite sintering material in the step contains various metal elements such as Si, Ba, Fe, Ca, Al and the like, and the chemical compositions of the porous multi-element alloy composite sintering material in each embodiment are shown in Table 3;
in the embodiment of the invention, the industrial waste residue comprises one or a mixture of more of silicon slag, barium slag and calcium slag, and the silicon slag comprises the following components: 60% -75% of SiO2、1％～4％Al2O31 to 3 percent of CaO, 1 to 8 percent of BaO, and the balance of ash and unreduced silica; the barium residue comprises the following components: 30 to 50 percent of SiO2、10％～40％BaO、2％～％20％CaO、1％～5％Al2O3The balance of the catalyst is ash and unreduced silicobarite; the calcium slag comprises the following components: 20 to 35 percent of SiO2、55％～70％CaO、1％～6％Al2O3The balance of ash, and the block-shaped dust removal powder is formed by briquetting and sintering the dust removal powder, and the chemical components of the raw materials in the specific embodiment are shown in Table 4.
Step 2: adding dedusting powder into the alloy solution in the step 1 through a metal conveying pipeline inserted into the furnace in a powder spraying manner, wherein the adding amount of the dedusting powder is at most 50% of the mass of the alloy raw material added in the step 1, and the amount of the dedusting powder sprayed in the powder spraying manner in the specific embodiment is shown in a table 2;
in the invention, at least one metal conveying pipe is adopted in the step, in the embodiment, one metal conveying pipe is adopted for spraying powder, the total flow of all the conveying pipes is 50-70 kg/min, dedusting powder is sprayed into the alloy liquid, the dedusting powder is conveyed into a refining furnace through a gas-solid two-phase mixing pipeline, the conveying pressure is 2-8 Mpa, and the metal conveying pipe in the step is inserted into a position which is at least 20cm away from the alloy liquid level; the flow rate and pressure of dust-removing powder injection and the height from the metal delivery pipe to the alloy liquid surface after being inserted into the alloy solution in the specific embodiment are shown in a table 7;
in the step, the chemical components and the content of the dust removal powder are 60 to 75 percent of SiO2、2％～10％BaO、1％～3％CaO、1％～5％Al2O3And the rest is ash, and the dust removal powder is micro silicon powder collected by a ferrosilicon smelting dust removal system and dust removal powder collected in a ferroalloy factory smelting process, wherein in the specific embodiment, the chemical components of the dust removal powder in the step are shown in table 5.
And step 3: and (3) sampling and assaying the alloy liquid, comparing the alloy liquid with the alloy components designed in the step (1), adding one or a mixture of several of dust removal powder, silicon slag, barium slag and calcium slag with corresponding mass according to the element content requirement until the chemical components of the smelted multi-element alloy reach the alloy components designed in the step (1), wherein the chemical components of the multi-element alloy obtained in each specific embodiment are shown in a table 6.
And tapping and pouring after the tested components of the multi-element alloy are qualified to form a multi-element alloy ingot, and crushing the multi-element alloy ingot into multi-element alloy particles or powder with different sizes according to the specification requirements of the order.
The implementation data of the specific example is as follows:
TABLE 1 examples step 1 alloy composition design
Si
Ba
Ca
Al
Example 1
72-75％
1-3％
1-2％
0.8-1.5％
Example 2
60-65％
4-6％
1.5-2％
2-3％
Example 3
70-72％
2-4％
2-3％
2.5-4％
Example 4
60-65％
6-10％
1.5-2％
2-3％
Comparative example 1
60-65％
6-10％
1.5-2％
2-3％
Comparative example 2
60-65％
6-10％
1.5-2％
2-3％
Comparative example 3
60-65％
6-10％
1.5-2％
2-3％
Comparative example 4
60-65％
6-10％
1.5-2％
2-3％
Table 2 examples step 1 and step 2 charging raw materials into a melting furnace and spraying dust removing powder
TABLE 3 examples the chemical composition of the porous multi-element alloy composite sinter in step 1
Chemical composition
Si
Ba
Ca
Al
Fe
Example 1
70-75
1-2
1-2
1-1.5
0
Example 2
60-70
3-5
1-3
2-4
1-2
Example 3
65-70
2-4
1-2
2-3
0
Example 4
60-75
5-10
1-2
2-3
1-3
Comparative example 1
60-75
5-10
1-2
2-3
1-3
Comparative example 2
60-75
5-10
1-2
2-3
1-3
Comparative example 3
60-75
5-10
1-2
2-3
1-3
Comparative example 4
60-75
5-10
1-2
2-3
1-3
TABLE 4 chemical composition of dust-removing powder, silicon slag, calcium slag and barium slag in lump form in step 1 of each example
TABLE 5 chemical composition of dusting powder in step 2 of each example
TABLE 6 composition of alloy finally obtained in step 3 of each example
Si
Ba
Ca
Al
Example 1
73.0
2.0
1.3
1.2
Example 2
64.0
4.3
1.8
2.5
Example 3
70
3
1.5
2.7
Example 4
61.3
6.8
1.8
2.3
Comparative example 1
63.3
7.4
1.7
1.7
Comparative example 2
64
8
1.8
2.5
Comparative example 3
64.5
9.1
1.9
2.5
Comparative example 4
64.7
9.2
1.7
2.6
TABLE 7 comparison of the effects of the examples
In some embodiments of the present invention, when the designed alloy is a high-calcium and high-barium alloy, the proportion of the calcium slag and the barium slag added in step 1 can be adjusted to be high.
In some comparative examples of the present invention, in step 1, since the amount of the raw material added is not reasonable, a large amount of metal oxide in the industrial waste residue cannot be reduced, so that the metal oxide cannot be melted into a metal liquid, and the metal oxide in the industrial waste residue floats on the alloy solution to form a very thick slag layer, which results in waste of the raw material.
In some comparative examples of the invention, in step 2, the addition amount of the dust removal powder is more than 50% of the mass of the alloy raw material added in step 1, so that a large amount of metal oxides in the dust removal powder cannot be reduced, metal elements cannot be blended into the alloy solution, and finally the dust removal powder floats on the upper layer of the alloy solution in the form of waste slag, thereby causing waste of the raw material.
While the foregoing embodiments have been described in terms of what are presently considered to be the most practical and preferred embodiments, it is to be understood that the invention is not to be limited to the disclosed embodiments, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.