CN114293043A - Method for smelting ferrovanadium alloy by ferrosilicon - Google Patents
Method for smelting ferrovanadium alloy by ferrosilicon Download PDFInfo
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- CN114293043A CN114293043A CN202111376053.XA CN202111376053A CN114293043A CN 114293043 A CN114293043 A CN 114293043A CN 202111376053 A CN202111376053 A CN 202111376053A CN 114293043 A CN114293043 A CN 114293043A
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- 238000003723 Smelting Methods 0.000 title claims abstract description 67
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910000628 Ferrovanadium Inorganic materials 0.000 title claims abstract description 54
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 48
- 239000000956 alloy Substances 0.000 title claims abstract description 48
- 229910000519 Ferrosilicon Inorganic materials 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000002893 slag Substances 0.000 claims abstract description 112
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 112
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 109
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 41
- 239000010431 corundum Substances 0.000 claims abstract description 41
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 34
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 27
- 239000010703 silicon Substances 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 19
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 19
- 239000004571 lime Substances 0.000 claims abstract description 19
- 238000007670 refining Methods 0.000 claims abstract description 19
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000005266 casting Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000007599 discharging Methods 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 abstract description 2
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract 1
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 238000010891 electric arc Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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Abstract
The invention relates to the technical field of metallurgy, and discloses a method for smelting ferrovanadium alloy by ferrosilicon. 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 furnace slag when the vanadium content in the smelted furnace slag is reduced to below 0.3%, 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; (2) repeating the step (1) and smelting for N times in stages, wherein N is more than or equal to 1; (3) adding vanadium pentoxide and iron for refining, when the content of vanadium in the ferrovanadium alloy liquid is 78-82%, 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 slag. The method can fully recover vanadium in the corundum slag, the vanadium recovery rate is high, and the vanadium content and the impurity content in the obtained ferrovanadium alloy are high.
Description
Technical Field
The invention relates to the technical field of metallurgy, in particular to a method for smelting ferrovanadium alloy by ferrosilicon.
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 ferrovanadium alloy by ferrosilicon.
In order to achieve the aim, the invention provides a method for smelting ferrovanadium alloy by ferrosilicon, 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 furnace slag when the vanadium content in the smelted furnace slag is reduced to below 0.3%, 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;
(2) repeating the step (1) and smelting for N times in stages, wherein N is more than or equal to 1;
(3) adding vanadium pentoxide and iron for refining, when the content of vanadium in the ferrovanadium alloy liquid is 78-82%, 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 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), the smelting temperature is 1700-1900 ℃, and the smelting time is 50-80 min.
Preferably, in step (1), the smelting furnace is a tiltable arc furnace.
Preferably, in the step (2), N is 1-10.
More preferably, in the step (2), N is 1 to 5.
Further preferably, in the step (2), N is 1 to 3.
Preferably, in the step (3), the refining temperature is 1800-2000 ℃, and the refining time is 20-40 min.
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 the slag when the vanadium content in the slag obtained by smelting is reduced to be below 0.3%, 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;
s2, mixing the vanadium-containing corundum slag, ferrosilicon and lime, adding the mixture into a smelting furnace, electrifying for smelting, and removing 80% of the slag when the vanadium content in the slag obtained by smelting is reduced to be below 0.3%, 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 iron for refining, discharging the slag and the ferrovanadium alloy liquid simultaneously when the content of vanadium in the ferrovanadium alloy liquid is 78-82%, and then casting and cooling the ferrovanadium alloy liquid to obtain ferrovanadium 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) and iron are used as refining mixture, the content of vanadium 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 in the vanadium-containing corundum slag can be fully recovered to prepare the ferrovanadium alloy with higher purity.
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 ferrosilicon 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 furnace slag when the vanadium content in the smelted furnace slag is reduced to below 0.3%, 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;
(2) repeating the step (1) and smelting for N times in stages, wherein N is more than or equal to 1;
(3) adding vanadium pentoxide and iron for refining, when the content of vanadium in the ferrovanadium alloy liquid is 78-82%, 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, vanadium-containing corundum slag, ferrosilicon and lime are mixed and then added into a smelting furnace for smelting, most of slag is removed when the vanadium content in the slag is reduced to a certain level (first stage), then the operations of feeding in stages and deslagging are carried out repeatedly according to the first stage mode, smelting is carried out for N times in stages (excluding the first stage), then refining mixture is added for smelting, when the vanadium content in a ferrovanadium alloy solution is 78-82%, the slag iron is discharged simultaneously, and casting and cooling are carried out, thus obtaining the high-vanadium iron and the 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, the charging proportion and the slag discharge standard are not required to be completely the same every time, as long as the addition amount of the ferrosilicon is 1.1-1.3 times of the theoretical value of the silicon mixing 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 be below 0.3%. The silicon coefficient theoretical value of the vanadium-containing corundum slag is calculated according to a chemical reaction formula.
In the present invention, the raw materials used need to be treated before smelting so that they meet the production requirements. 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 a specific embodiment, the ferrosilicon may be 75 ferrosilicon, and the chemical composition of the 75 ferrosilicon is 72 to 77 mass% of silicon.
In the method of the present invention, in the step (1), the smelting process parameters may be conventional in the art. In a specific embodiment, in the step (1), the smelting temperature is 1700 to 1900 ℃, such as 1700 ℃, 1750 ℃, 1800 ℃, 1850 ℃ or 1900 ℃; the smelting time is 50-80 min, such as 50min, 55min, 60min, 65min, 70min, 75min or 80 min. In a preferred embodiment, in the step (1), the smelting temperature is 1800 ℃ and the smelting time is 50 min.
In the method according to the invention, the smelting furnace may be a conventional choice in the art. In a preferred embodiment, in step (1), 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 (1) in the step (2) may be determined according to the capacity of the smelting furnace.
In a specific embodiment, in the step (2), N is 1 to 10. In a preferred embodiment, in the step (2), N is 1 to 5, and more preferably, N is 1 to 3. N is a positive integer not less than 1.
In the method of the present invention, the refining process parameters may be performed according to conventional operations in the art. In specific embodiments, in step (3), the refining temperature is 1800 to 2000 ℃, such as 1800 ℃, 1850 ℃, 1900 ℃, 1950 ℃ or 2000 ℃; the refining time is 20-40 min, such as 20min, 25min, 30min, 35min or 40 min. In a preferred embodiment, in step (3), the refining temperature is 1900 ℃ and the refining time is 30 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 the slag when the vanadium content in the slag obtained by smelting is reduced to be below 0.3%, 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;
s2, mixing the vanadium-containing corundum slag, ferrosilicon and lime, adding the mixture into a smelting furnace, electrifying for smelting, and removing 80% of the slag when the vanadium content in the slag obtained by smelting is reduced to be below 0.3%, 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 iron for refining, discharging the slag and the ferrovanadium alloy liquid simultaneously when the content of vanadium in the ferrovanadium alloy liquid is 78-82%, and then casting and cooling the ferrovanadium alloy liquid to obtain ferrovanadium 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), 747kg 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 1.10, after the materials are electrified and smelted at 1800 ℃ for 50min, a slag sample is taken for analysis, and 5000kg of slag is discharged when the content of residual vanadium in the slag is 0.26 percent;
2) 5000kg of vanadium-containing corundum slag (containing 4 percent of vanadium), 493kg 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 ℃ by electrifying, a slag sample is taken for analysis, and 5500kg of slag is discharged when the residual vanadium in the slag is 0.22 percent;
3) 77kg of tablets are addedVanadium (V)2O598.3 percent of mass content), 10kg of iron is electrified and refined for 30min at 1900 ℃, then the vanadium residue in the slag is 4 percent, the vanadium content in the ferrovanadium alloy liquid is 79.3 percent, the vanadium is discharged from a furnace and cast, and then the vanadium-iron alloy is cooled to room temperature along with an ingot mold, thus obtaining the ferrovanadium alloy.
A ferrovanadium alloy sample is taken for analysis, wherein the vanadium content is 79.3 percent, the iron content is 17 percent, the silicon content is 0.1 percent, and the vanadium yield is 97.0 percent.
Example 2
1) 6000kg of vanadium-containing corundum slag (containing 5 percent of vanadium), 814kg 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 1.20, after the vanadium-containing corundum slag is electrified and smelted at 1800 ℃ for 50min, a slag sample is taken for analysis, and 5000kg of slag is discharged when the content of residual vanadium in the slag is 0.16 percent;
2) 5000kg of vanadium-containing corundum slag (containing 4 percent of vanadium), 537kg 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 ℃ by electrifying, a slag sample is taken for analysis, and 5500kg of slag is discharged when the residual vanadium in the slag is 0.12 percent;
3) 156kg of flake vanadium (V) was added2O598% by mass), 10kg of iron; electrifying to smelt at 1900 ℃ for 30min, quickly analyzing, taking out the slag with residual vanadium of 3.5% and vanadium content in ferrovanadium alloy liquid of 80.1%, casting, and cooling to room temperature along with an ingot mold to obtain ferrovanadium.
A ferrovanadium alloy sample is taken for analysis, wherein the vanadium content is 80.1 percent, the iron content is 16 percent, the silicon content is 0.2 percent, and the vanadium yield is 98 percent.
Example 3
1) 6000kg of vanadium-containing corundum slag (containing 5 percent of vanadium), 881kg 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 1.30, after the materials are electrified and smelted at 1800 ℃ for 50min, a slag sample is taken for analysis, and 5000kg of slag is discharged when the residual vanadium in the slag is 0.1 percent;
2) 5000kg of vanadium-containing corundum slag (containing 4 percent of vanadium), 581kg of 75 silicon iron (containing 80 percent of silicon) and 150kg of lime are added, the mixture is electrified and 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 0.12 percent;
3) 235kg of flake vanadium (V) was added2O598 percent of mass content), 10kg of iron is electrified and smelted for 30min at 1900 ℃, then the vanadium residue in the slag is 3 percent, the vanadium content in the ferrovanadium alloy liquid is 80.3 percent, the vanadium is discharged from a furnace and cast, and then the vanadium-iron alloy is cooled to room temperature along with an ingot mold, thus obtaining the ferrovanadium alloy.
A ferrovanadium alloy sample is taken for analysis, wherein the vanadium content is 80.3 percent, the iron content is 16.2 percent, the silicon content is 0.2 percent, and the vanadium yield is 98.2 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. The method for smelting ferrovanadium alloy by ferrosilicon 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 furnace slag when the vanadium content in the smelted furnace slag is reduced to below 0.3%, 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;
(2) repeating the step (1) and smelting for N times in stages, wherein N is more than or equal to 1;
(3) adding vanadium pentoxide and iron for refining, when the content of vanadium in the ferrovanadium alloy liquid is 78-82%, 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 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 according to claim 1, wherein in the step (1), the smelting temperature is 1700-1900 ℃, and the smelting time is 50-80 min.
5. The method according to claim 1, characterized in that in step (1), the smelting furnace is a tiltable arc furnace.
6. The method according to claim 1, wherein in the step (2), N is 1 to 10.
7. The method according to claim 6, wherein in the step (2), N is 1 to 5.
8. The method according to claim 7, wherein in the step (2), N is 1 to 3.
9. The method according to claim 1, wherein in the step (3), 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 the slag when the vanadium content in the slag obtained by smelting is reduced to be below 0.3%, 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;
s2, mixing the vanadium-containing corundum slag, ferrosilicon and lime, adding the mixture into a smelting furnace, electrifying for smelting, and removing 80% of the slag when the vanadium content in the slag obtained by smelting is reduced to be below 0.3%, 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 iron for refining, discharging the slag and the ferrovanadium alloy liquid simultaneously when the content of vanadium in the ferrovanadium alloy liquid is 78-82%, and then casting and cooling the ferrovanadium alloy liquid to obtain ferrovanadium and vanadium-containing slag.
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