CN114350962A - Method for smelting ferrovanadium alloy from vanadium-containing corundum slag - Google Patents
Method for smelting ferrovanadium alloy from vanadium-containing corundum slag Download PDFInfo
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Abstract
The invention relates to the technical field of metallurgy, and discloses a method for smelting a ferrovanadium alloy from vanadium-containing corundum slag. The method comprises the following steps: (1) mixing vanadium-containing corundum slag, ferrosilicon and lime, adding the mixture into a smelting furnace, electrifying for smelting, and removing 80% of slag when the vanadium content in the slag is reduced to below 0.1%, wherein the adding amount of the ferrosilicon is 1.5-1.7 times of the theoretical value of the silicon-blending coefficient; (2) adding vanadium-containing corundum slag, ferrosilicon and lime, electrifying for smelting, and removing 80% of slag when the vanadium content in the slag is reduced to below 0.1%, wherein the adding amount of the ferrosilicon is 1.1-1.3 times of the theoretical value of the silicon-blending coefficient; (3) repeating the step (2) and smelting for N times in stages; (4) adding vanadium pentoxide, lime and iron for refining, taking out slag iron when the vanadium content in the ferrovanadium alloy liquid is 48-52%, casting and cooling to obtain ferrovanadium and vanadium-containing slag. The method can fully recover vanadium in the corundum slag, and the obtained ferrovanadium alloy has high vanadium content and low impurity content.
Description
Technical Field
The invention relates to the technical field of metallurgy, in particular to a method for smelting a ferrovanadium alloy from vanadium-containing corundum slag.
Background
Vanadium plays a role in deoxidizing and refining grains in steel, and a small amount of vanadium can improve the performance of the steel and improve the wear resistance, toughness and strength of the steel. The ferrovanadium (ferrovanadium alloy) is a main alloy additive for smelting vanadium-containing steel because of the advantages of high alloying degree, high vanadium yield, low impurity content and the like.
At present, most ferrovanadium manufacturers in China adopt a one-step electro-aluminothermic smelting process, prepared furnace burden is electrified and arc-ignited in an electric furnace to react to generate metal vanadium and aluminum oxide and emit heat, the aluminum oxide is combined with a slag former added into the furnace burden to form low-melting-point and low-density furnace slag, and iron particles added into the furnace burden are melted to form an infinite solid solution with the vanadium; the added slag former can reduce the melting point of the slag and improve the alkalinity of the melt, and is beneficial to alloy settlement. Because the density difference between the alloy and the slag is large, the slag and the ferrovanadium alloy are automatically layered in a molten state, and the ferrovanadium alloy is obtained by separating slag after full condensation. The vanadium content in the smelted corundum slag is more than 2.0 percent, so that the vanadium cannot be effectively recycled.
Disclosure of Invention
The invention aims to solve the problem that the vanadium in the corundum slag obtained by the one-step electro-aluminothermic vanadium iron smelting process in the prior art is not reasonably utilized, and provides a method for smelting a vanadium-iron alloy by using vanadium-containing corundum slag.
In order to achieve the aim, the invention provides a method for smelting ferrovanadium alloy from vanadium-containing corundum slag, which comprises the following steps:
(1) mixing vanadium-containing corundum slag, ferrosilicon and lime, adding the mixture into a smelting furnace, electrifying for smelting, and removing 80% of slag when the vanadium content in the slag obtained by smelting is reduced to be below 0.1%, wherein the adding amount of the ferrosilicon is 1.5-1.7 times of the theoretical value of the silicon coefficient of the vanadium-containing corundum slag;
(2) mixing vanadium-containing corundum slag, ferrosilicon and lime, adding the mixture into a smelting furnace, electrifying for smelting, and removing 80% of slag when the vanadium content in the slag obtained by smelting is reduced to be below 0.1%, wherein the adding amount of the ferrosilicon is 1.1-1.3 times of the theoretical value of the silicon coefficient of the vanadium-containing corundum slag;
(3) repeating the step (2) and smelting for N times in stages, wherein N is more than or equal to 0;
(4) adding vanadium pentoxide, lime and iron for refining, when the content of vanadium in the ferrovanadium alloy liquid is 48-52%, simultaneously discharging the furnace slag and the ferrovanadium alloy liquid, and then casting and cooling the ferrovanadium alloy liquid to obtain ferrovanadium alloy and vanadium-containing slag.
Preferably, the content of TV in the vanadium-containing corundum slag is more than 2 wt%.
Preferably, the ferrosilicon is 75 ferrosilicon.
Preferably, in the step (1) and the step (2), the smelting temperature is 1700-1900 ℃, and the smelting time is 50-70 min.
Preferably, the smelting furnace is a tiltable arc furnace.
Preferably, in the step (3), N is 0 to 10.
More preferably, in the step (3), N is 0 to 5.
Further preferably, in the step (3), N is 0 to 3.
Preferably, in the step (4), the refining temperature is 1800-.
Preferably, the method comprises the steps of:
s1, mixing the vanadium-containing corundum slag, ferrosilicon and lime, adding the mixture into a smelting furnace, electrifying for smelting, and removing 80% of slag when the vanadium content in the slag obtained by smelting is reduced to be below 0.1%, wherein the adding amount of the ferrosilicon is 1.5-1.7 times of the theoretical value of the silicon coefficient of the vanadium-containing corundum slag;
s2, mixing the vanadium-containing corundum slag, ferrosilicon and lime, adding the mixture into a smelting furnace, electrifying for smelting, and removing 80% of slag when the vanadium content in the slag obtained by smelting is reduced to be below 0.1%, wherein the adding amount of the ferrosilicon is 1.1-1.3 times of the theoretical value of the silicon coefficient of the vanadium-containing corundum slag;
and S3, adding vanadium pentoxide and lime for refining, discharging the slag and the ferrovanadium alloy liquid simultaneously when the content of vanadium in the ferrovanadium alloy liquid is 48-52%, and then casting and cooling the ferrovanadium alloy liquid to obtain ferrovanadium alloy and vanadium-containing slag.
The method takes vanadium-containing corundum slag and ferrosilicon as raw materials, simultaneously ferrosilicon is taken as a reducing agent, lime is used for adjusting the alkalinity of an alloy solution, multi-stage smelting is carried out, and the vanadium content in the slag is controlled; meanwhile, vanadium pentoxide (desiliconization agent), lime and iron are used as refining mixture, the content of silicon in the ferrovanadium alloy liquid is controlled, the energy can be saved by using the waste heat of the last smelting stage for the next smelting stage, and the vanadium of the vanadium-containing corundum slag can be fully recovered to prepare the ferrovanadium alloy meeting the national standard.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The method for smelting ferrovanadium alloy by using vanadium-containing corundum slag provided by the invention comprises the following steps:
(1) mixing vanadium-containing corundum slag, ferrosilicon and lime, adding the mixture into a smelting furnace, electrifying for smelting, and removing 80% of slag when the vanadium content in the slag obtained by smelting is reduced to be below 0.1%, wherein the adding amount of the ferrosilicon is 1.5-1.7 times of the theoretical value of the silicon coefficient of the vanadium-containing corundum slag;
(2) mixing vanadium-containing corundum slag, ferrosilicon and lime, adding the mixture into a smelting furnace, electrifying for smelting, and removing 80% of slag when the vanadium content in the smelted slag is reduced to below 0.1%, wherein the adding amount of the ferrosilicon is 1.1-1.3 times of the theoretical value of the silicon coefficient of the vanadium-containing corundum slag;
(3) repeating the step (2) and smelting for N times in stages, wherein N is more than or equal to 0;
(4) adding vanadium pentoxide, lime and iron for refining, when the content of vanadium in the ferrovanadium alloy liquid is 48-52%, simultaneously discharging the furnace slag and the ferrovanadium alloy liquid, and then casting and cooling the ferrovanadium alloy liquid to obtain ferrovanadium and vanadium-containing rich slag.
In the invention, firstly mixing vanadium-containing corundum slag, ferrosilicon (with silicon coefficient of 1.5-1.7) and lime, adding the mixture into a smelting furnace for smelting, and removing most of slag when the vanadium content in the slag is reduced to 0.1% (first stage); then feeding and deslagging according to a first-stage mode, except that the silicon preparation coefficient is 1.1-1.3; and then, carrying out periodic charging and slag discharging repeated operation according to a mode of a second period, carrying out periodic smelting for N times (N is more than or equal to 0 and does not include the second period), then adding a refined mixture of vanadium pentoxide, lime and iron for smelting, discharging slag iron when the vanadium content in the ferrovanadium alloy solution is 48-52%, casting and cooling to obtain high-vanadium iron and vanadium-containing slag. The vanadium-containing slag can be used as a raw material to continue smelting according to the method of the invention, and vanadium in the vanadium-containing corundum slag is recovered to the maximum extent. In the stage smelting process of the step (3), the charging proportion and the slag discharge standard are not required to be completely the same every time, as long as the adding amount of the ferrosilicon is 1.1-1.3 times of the theoretical value of the silicon coefficient of the vanadium-containing corundum slag, and 80% of the slag is removed when the vanadium content in the slag obtained by smelting is reduced to below 0.1%. The silicon coefficient theoretical value of the vanadium-containing corundum slag refers to the calculated value of a chemical reaction formula.
In the invention, the silicon distribution coefficient of the first stage smelting is 1.5-1.7, and the silicon distribution coefficient of the second stage smelting and the later stage smelting is 1.1-1.3, so that the reason for setting is that the excessive reducing agent is that vanadium in the slag is reduced to the maximum extent.
60 in the invention, the addition amount of lime and vanadium pentoxide is determined according to specific conditions.
In a specific embodiment, the vanadium-containing corundum slag employed in the present invention has a TV content of > 2 wt.%. Except Al in the vanadium-containing corundum slag2O3And also contains MgO.
In the method, the ferrosilicon can be used as a reducing agent to reduce high-valence vanadium in the vanadium-containing corundum slag. In particular embodiments, the ferrosilicon may be 75 ferrosilicon, with the chemical composition of 75 ferrosilicon being 72-75 wt.% silicon.
In the method of the present invention, in the step (1) and the step (2), the smelting process parameters can be the conventional operation in the field. In a specific embodiment, in the step (1) and the step (2), the smelting temperature is 1700-1900 ℃, and for example, may be 1700 ℃, 1750 ℃, 1800 ℃, 1850 ℃ or 1900 ℃; the smelting time is 50-70min, for example, 50min, 55min, 60min, 65min or 70 min.
In the method according to the invention, the smelting furnace may be a conventional choice in the art. In a preferred embodiment, the smelting furnace is a tiltable arc furnace.
In the method of the present invention, the number of times of performing the periodical smelting by repeating the step (2) in the step (3) may be determined according to the capacity of the smelting furnace.
In a specific embodiment, in the step (3), N is 0 to 10. In a preferred embodiment, in step (3), N is 0 to 5, more preferably, N is 0 to 3. N is an integer of 0 or more.
In the method of the present invention, the refining process parameters may be performed according to conventional operations in the art. In a specific embodiment, in the step (4), the refining temperature is 1800-; the refining time is 20-40min, such as 20min, 25min, 30min, 35min or 40 min.
In one embodiment, the method of the present invention comprises the steps of:
s1, mixing the vanadium-containing corundum slag, ferrosilicon and lime, adding the mixture into a smelting furnace, electrifying for smelting, and removing 80% of slag when the vanadium content in the slag obtained by smelting is reduced to be below 0.1%, wherein the adding amount of the ferrosilicon is 1.5-1.7 times of the theoretical value of the silicon coefficient of the vanadium-containing corundum slag;
s2, mixing the vanadium-containing corundum slag, ferrosilicon and lime, adding the mixture into a smelting furnace, electrifying for smelting, and removing 80% of slag when the vanadium content in the slag obtained by smelting is reduced to be below 0.1%, wherein the adding amount of the ferrosilicon is 1.1-1.3 times of the theoretical value of the silicon coefficient of the vanadium-containing corundum slag;
and S3, adding vanadium pentoxide, lime and iron for refining, discharging the slag and the ferrovanadium alloy liquid simultaneously when the content of vanadium in the ferrovanadium alloy liquid is 48-52%, and then casting and cooling the ferrovanadium alloy liquid to obtain ferrovanadium alloy and vanadium-containing slag.
The present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.
Example 1
1) 6000kg of vanadium-containing corundum slag (containing 5 percent of vanadium), 1018kg of 75 silicon iron (containing 80 percent of silicon) and 200kg of lime are uniformly mixed and then added into a tiltable electric arc furnace, the silicon distribution coefficient is 1.50, after the vanadium-containing corundum slag is electrified and smelted at 1800 ℃ for 60min, a slag sample is taken for analysis, and 5000kg of slag is discharged when the content of residual vanadium in the slag is below 0.1 percent;
2) 5000kg of vanadium-containing corundum slag (containing 4 percent of vanadium), 582kg of 75 silicon iron (containing 80 percent of silicon), 150kg of lime, 1.30 of silicon coefficient, electrifying for smelting at 1800 ℃ for 50min, taking a slag sample for analysis, and discharging 5500kg of slag when the residual vanadium in the slag is below 0.1 percent;
3) 616kg of vanadium flake (V) was added2O598.3 percent of lime and 670kg of iron, electrifying, refining at 1900 ℃ for 20min, quickly analyzing, obtaining 2.8 percent of residual vanadium in slag and 51.1 percent of vanadium in ferrovanadium alloy liquid, discharging and casting, and then cooling to room temperature along with an ingot mold to obtain the ferrovanadium alloy.
Analyzing a ferrovanadium alloy sample, wherein the vanadium content is 51.1%, the iron content is 47.2%, and the silicon content is 0.3%; the vanadium yield was 98.5%.
Example 2
1) 6000kg of vanadium-containing corundum slag (containing 5 percent of vanadium), 1085kg of 75 silicon iron (containing 80 percent of silicon) and 200kg of lime are uniformly mixed and then added into a tiltable electric arc furnace, the silicon distribution coefficient is 1.60, after the furnace is electrified and smelted at 1800 ℃ for 60min, a slag sample is taken for analysis, and 5000kg of slag is discharged when the content of vanadium residues in the slag is below 0.1 percent;
2) 5000kg of vanadium-containing corundum slag (containing 4 percent of vanadium), 492kg of 75 silicon iron (containing 80 percent of silicon) and 150kg of lime are added, the coefficient of silicon is 1.20, after the materials are smelted for 50min at 1800 ℃, a slag sample is taken for analysis, and 5500kg of slag is discharged when the residual vanadium in the slag is below 0.1 percent;
3) join 625kg of vanadium (V) flakes2O5Content 98%), 100kg of lime and 670kg of iron; electrifying to smelt at 1900 ℃ for 20min, quickly analyzing, wherein the content of residual vanadium in slag is 3.5%, the content of vanadium in the ferrovanadium alloy liquid is 50.2%, discharging and casting, and then cooling to room temperature along with the ingot mold to obtain the ferrovanadium alloy.
A ferrovanadium alloy sample is taken for analysis, wherein the vanadium content is 50.2 percent, the iron content is 48.1 percent, the silicon content is 0.2 percent, and the vanadium yield is 98.3 percent.
Example 3
1) 6000kg of vanadium-containing corundum slag (containing 5 percent of vanadium), 1331kg of 75 silicon iron (containing 80 percent of silicon) and 200kg of lime are uniformly mixed and then added into a tiltable electric arc furnace, the silicon distribution coefficient is 1.70, after the vanadium-containing corundum slag is smelted for 60min at 1800 ℃, a slag sample is taken for analysis, and 5000kg of slag is discharged when the content of residual vanadium in the slag is below 0.1 percent;
2) 5000kg of vanadium-containing corundum slag (containing 4 percent of vanadium), 582kg of 75 silicon iron (containing 80 percent of silicon) and 150kg of lime are added, the coefficient of silicon is 1.10, after the materials are smelted for 50min at 1800 ℃, a slag sample is taken for analysis, and 5500kg of slag is discharged when the residual vanadium in the slag is below 0.1 percent;
3) 625kg of flake vanadium (V) was added2O598.3 percent of lime and 670kg of iron, electrifying, smelting at 1900 ℃ for 20min, quickly analyzing, obtaining 4 percent of residual vanadium in slag and 49.5 percent of vanadium in ferrovanadium alloy liquid, discharging and casting, and then cooling to room temperature along with an ingot mold to obtain ferrovanadium alloy.
A ferrovanadium alloy sample is taken for analysis, wherein the vanadium content is 49.5 percent, the iron content is 48.1 percent, the silicon content is 0.1 percent, and the vanadium yield is 98.3 percent.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A method for smelting ferrovanadium alloy from vanadium-containing corundum slag is characterized by comprising the following steps:
(1) mixing vanadium-containing corundum slag, ferrosilicon and lime, adding the mixture into a smelting furnace, electrifying for smelting, and removing 80% of slag when the vanadium content in the slag obtained by smelting is reduced to be below 0.1%, wherein the adding amount of the ferrosilicon is 1.5-1.7 times of the theoretical value of the silicon coefficient of the vanadium-containing corundum slag;
(2) mixing vanadium-containing corundum slag, ferrosilicon and lime, adding the mixture into a smelting furnace, electrifying for smelting, and removing 80% of slag when the vanadium content in the slag obtained by smelting is reduced to be below 0.1%, wherein the adding amount of the ferrosilicon is 1.1-1.3 times of the theoretical value of the silicon coefficient of the vanadium-containing corundum slag;
(3) repeating the step (2) and smelting for N times in stages, wherein N is more than or equal to 0;
(4) adding vanadium pentoxide, lime and iron for refining, when the content of vanadium in the ferrovanadium alloy liquid is 48-52%, simultaneously discharging the furnace slag and the ferrovanadium alloy liquid, and then casting and cooling the ferrovanadium alloy liquid to obtain ferrovanadium alloy and vanadium-containing slag.
2. A method according to claim 1, characterized in that the vanadium-containing corundum slag has a TV content of > 2 wt.%.
3. The method of claim 1, wherein the ferrosilicon is 75 ferrosilicon.
4. The method as claimed in claim 1, wherein in the steps (1) and (2), the smelting temperature is 1700-1900 ℃, and the smelting time is 50-70 min.
5. The method according to claim 1, characterized in that said smelting furnace is a tiltable arc furnace.
6. The method according to claim 1, wherein in the step (3), N is 0 to 10.
7. The method according to claim 6, wherein in the step (3), N is 0 to 5.
8. The method according to claim 7, wherein in the step (3), N is 0 to 3.
9. The method as claimed in claim 1, wherein in step (4), the refining temperature is 1800-2000 ℃ and the refining time is 20-40 min.
10. Method according to claim 6, characterized in that it comprises the following steps:
s1, mixing the vanadium-containing corundum slag, ferrosilicon and lime, adding the mixture into a smelting furnace, electrifying for smelting, and removing 80% of slag when the vanadium content in the slag obtained by smelting is reduced to be below 0.1%, wherein the adding amount of the ferrosilicon is 1.5-1.7 times of the theoretical value of the silicon coefficient of the vanadium-containing corundum slag;
s2, mixing the vanadium-containing corundum slag, ferrosilicon and lime, adding the mixture into a smelting furnace, electrifying for smelting, and removing 80% of slag when the vanadium content in the slag obtained by smelting is reduced to be below 0.1%, wherein the adding amount of the ferrosilicon is 1.1-1.3 times of the theoretical value of the silicon coefficient of the vanadium-containing corundum slag;
and S3, adding vanadium pentoxide, lime and iron for refining, discharging the slag and the ferrovanadium alloy liquid simultaneously when the content of vanadium in the ferrovanadium alloy liquid is 48-52%, and then casting and cooling the ferrovanadium alloy liquid to obtain ferrovanadium alloy and vanadium-containing slag.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115800A (en) * | 2011-01-14 | 2011-07-06 | 河北钢铁股份有限公司承德分公司 | Pollution-free production process for ferrovanadium alloy |
| CN105886787A (en) * | 2016-05-13 | 2016-08-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for recycling vanadium from vanadium-containing corundum slags |
| CN107058764A (en) * | 2017-04-17 | 2017-08-18 | 攀钢集团研究院有限公司 | A kind of method that vanadium is reclaimed from corundum slag |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115800A (en) * | 2011-01-14 | 2011-07-06 | 河北钢铁股份有限公司承德分公司 | Pollution-free production process for ferrovanadium alloy |
| CN105886787A (en) * | 2016-05-13 | 2016-08-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for recycling vanadium from vanadium-containing corundum slags |
| CN107058764A (en) * | 2017-04-17 | 2017-08-18 | 攀钢集团研究院有限公司 | A kind of method that vanadium is reclaimed from corundum slag |
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