CN113265577A - Method for preparing FeV50 alloy from waste iron materials in vanadium extraction from vanadium slag - Google Patents
Method for preparing FeV50 alloy from waste iron materials in vanadium extraction from vanadium slag Download PDFInfo
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Abstract
The invention relates to the field of metallurgy, and discloses a method for preparing FeV50 alloy by using waste iron materials from vanadium extraction from vanadium slag, which comprises the following steps: uniformly mixing vanadium oxide, aluminum particles, vanadium slag vanadium-extracting waste iron materials, scrap iron and lime to obtain a ferrovanadium smelting mixture, uniformly loading the ferrovanadium smelting mixture into a smelting electric furnace for smelting, air-cooling a furnace body after smelting is finished, and then disassembling the furnace to obtain FeV50 alloy and smelting slag. The method fully utilizes the composition characteristics and cost advantages of the waste iron materials in the vanadium extraction process of the vanadium slag, and the finally produced ferrovanadium alloy product is qualified in composition and good in quality.
Description
Technical Field
The invention relates to the field of metallurgy, in particular to a method for preparing FeV50 alloy by using waste iron materials in vanadium extraction from vanadium slag.
Background
The ferrovanadium alloy is widely applied to vanadium-containing microalloy steel and has a dual strengthening mechanism of fine grain strengthening and precipitation strengthening, so that the overheating sensitivity is reduced, and the strength and the wear resistance of steel are improved. The method is widely applied to industries such as buildings, aerospace, roads and bridges and the like. The ferrovanadium alloy is produced mainly by a silicothermic method, an aluminothermic method, a carbothermic method and other thermal reduction methods. Because the reduction activity of the aluminum is stronger, the heat productivity in the reduction process is large, and the aluminothermic reduction is most widely applied.
At present, ferrovanadium smelting methods in the world can be divided into a one-step method, a two-step method and a multi-stage method. Wherein, the one-step smelting process is simple, but the vanadium yield is relatively low, and the product quality is controlled by the raw material quality and the batching precision; the two-step method is mainly characterized in that after the vanadium-containing material is subjected to enhanced reduction by adding excessive reducing agents, the excessive reducing agents in the alloy are further removed by refining, so that the purpose of reducing the vanadium loss in slag is achieved; the multi-stage method is based on the two-stage method, and realizes the reduction of vanadium loss in smelting slag and the improvement of smelting efficiency through the operations of aluminum distribution in stages, feeding in batches and slag discharging for many times, and enhances the stability of a smelting system to a certain extent.
However, whatever smelting process and equipment are adopted, the iron required by the production of the ferrovanadium alloy at present is mainly high-purity iron particles or scrap steel or scrap iron produced in the steelmaking process, and the total amount of iron and oxygen is generally higher than 95%. Patent application CN103757171A discloses a method for smelting high-vanadium iron, which uses cold-rolled steel scrap as iron raw material, the iron raw material has the advantages of high iron content, low impurity content, and stable vanadium iron alloy composition, but has the disadvantages of high price and high vanadium iron production cost and pressure. Patent application 104878273A discloses a method for smelting ferrovanadium by using iron particles and steel scraps, in the method, ball-milled iron particles generated by processing vanadium slag are used for replacing part of steel scraps to smelt ferrovanadium, the method utilizes ball-milled iron particles with relatively low price in the process, the production cost of ferrovanadium is reduced to a certain extent, but certain slag inclusion exists in the ball-milled iron particles, and the qualification rate of ferrovanadium products is easily influenced. Patent application CN 107739968A discloses a method for producing ferrovanadium alloy by using iron scale to replace steel scrap in the prior art and to produce ferrovanadium alloy, which makes full use of the cost advantage of iron scale, but needs to consume a large amount of expensive reducing agent.
Disclosure of Invention
The invention aims to solve the problems of high cost and poor quality of ferrovanadium alloy in the production process of ferrovanadium alloy in the prior art, and provides a method for preparing FeV50 alloy by using waste iron materials from vanadium slag vanadium extraction.
In order to achieve the aim, the invention provides a method for preparing FeV50 alloy by using waste iron materials in vanadium extraction from vanadium slag, which comprises the following steps: uniformly mixing vanadium oxide, aluminum particles, vanadium slag vanadium extraction waste iron materials, scrap iron and lime to obtain a ferrovanadium smelting mixture, uniformly loading the ferrovanadium smelting mixture into a smelting electric furnace for smelting, air-cooling a furnace body after smelting is finished, and then disassembling the furnace to obtain FeV50 alloy and smelting slag;
the chemical composition of the vanadium-extracting waste iron material of the vanadium slag is as follows: more than or equal to 79 weight percent of TFe, more than or equal to 1 weight percent of TV, less than or equal to 2 weight percent of Ti, less than or equal to 2 weight percent of Si, and less than or equal to 2 weight percent of Mn;
the mass ratio of the vanadium oxide to the aluminum particles to the waste iron materials for extracting vanadium from the vanadium slag to the scrap iron to the lime is 100:35-55:20-80:0-60: 10-20;
the mass ratio of the waste iron materials for extracting vanadium from the vanadium slag to the scrap iron is 5: 0-10.
Preferably, the mass ratio of the waste iron materials for extracting vanadium from the vanadium slag to the scrap iron is 5: 3-8.
Preferably, the waste iron material for vanadium extraction from the vanadium slag is at least one of coarse vanadium slag ball-milled iron particles, refined vanadium slag winnowing magnetic materials and leached tailings iron-rich aggregates.
Preferably, in the waste iron material for extracting vanadium from vanadium slag, the mass ratio of metallic state Fe to oxidized state Fe is 4-10: 1.
Preferably, the vanadium oxide is vanadium trioxide and/or vanadium pentoxide.
Further preferably, TV in the vanadium trioxide is more than or equal to 63 wt%, and TV in the vanadium pentoxide is more than or equal to 54 wt%.
Further preferably, the vanadium oxide is vanadium trioxide or a mixture of vanadium pentoxide and vanadium trioxide.
Further preferably, the mass ratio of the vanadium pentoxide to the vanadium trioxide is 2: 0.9-8.
Preferably, the purity of the aluminum particles is more than or equal to 99 weight percent, and the particle size of the aluminum particles is 0.1-1 cm.
Preferably, the purity of the scrap iron is more than or equal to 99 weight percent, and the surface area of the scrap iron is less than or equal to 5cm2。
Preferably, the content of CaO in the lime is more than or equal to 80 weight percent, and the content of metal impurities in the lime is less than or equal to 1 weight percent.
Preferably, the smelting comprises the following specific processes: and lowering the electrode to be in contact with the materials, electrifying to strike an arc, triggering a reaction, igniting and smelting, and continuously electrifying until smelting is finished after the ferrovanadium smelting mixture is completely melted to form a molten pool and no obvious crust is formed on the surface of the molten pool.
Further preferably, the vanadium content reduction range in the smelting slag is less than or equal to 0.05 weight percent/min as a standard after smelting.
Preferably, the unit alloy power supply power in the continuous electrifying process is 400-600 kVA/t.
The method fully utilizes the component advantages of the vanadium-extracting waste iron material of the vanadium slag, not only can efficiently utilize the main element iron in the vanadium-extracting waste iron material of the vanadium slag, but also fully extracts the vanadium in the vanadium-extracting waste iron material of the vanadium slag, and finally the vanadium-iron alloy product obtained by production is qualified in component and good in quality, so that the comprehensive utilization of the vanadium-and iron-containing waste resources is realized, and the production cost of the vanadium-iron alloy is reduced.
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 invention provides a method for preparing FeV50 alloy by using waste iron materials in vanadium extraction from vanadium slag, which comprises the following steps: uniformly mixing vanadium oxide, aluminum particles, vanadium slag vanadium extraction waste iron materials, scrap iron and lime to obtain a ferrovanadium smelting mixture, uniformly loading the ferrovanadium smelting mixture into a smelting electric furnace for smelting, air-cooling a furnace body after smelting is finished, and then disassembling the furnace to obtain FeV50 alloy and smelting slag;
the chemical composition of the vanadium-extracting waste iron material of the vanadium slag is as follows: more than or equal to 79 weight percent of TFe, more than or equal to 1 weight percent of TV, less than or equal to 2 weight percent of Ti, less than or equal to 2 weight percent of Si, and less than or equal to 2 weight percent of Mn;
the mass ratio of the vanadium oxide to the aluminum particles to the waste iron materials for extracting vanadium from the vanadium slag to the scrap iron to the lime is 100:35-55:20-80:0-60: 10-20;
the mass ratio of the waste iron materials for extracting vanadium from the vanadium slag to the scrap iron is 5: 0-10.
In the present invention, TFe means the total Fe content, and TV means the total V content.
In the invention, the cost can be saved by extracting vanadium from the vanadium slag and recycling the vanadium in the part of materials due to excessive waste iron materials, but the poor slag effect is adversely affected and the impurity components of the alloy are possibly overproof.
Under the preferable condition, the mass ratio of the waste iron materials for extracting vanadium from the vanadium slag to the scrap iron is 5: 3-8. Specifically, the mass ratio of the waste iron materials for extracting vanadium from the vanadium slag to the scrap iron can be 5: 3. 5: 3.5 and 5: 4. 5: 4.5, 5: 5. 5: 5.5, 5: 6. 5: 6.5, 5: 7. 5: 7.5 or 5: 8. further preferably, the purity of the scrap iron is more than or equal to 99 weight percent, and the surface area of the scrap iron is less than or equal to 5cm2. Specifically, the surface area of the iron pieces may beIs 0.5cm2、1cm2、1.5cm2、2cm2、2.5cm2、3cm2、3.5cm2、4cm2、4.5cm2Or 5cm2。
In the invention, the waste iron material for extracting vanadium from vanadium slag is at least one of coarse vanadium slag ball-milled iron particles, refined vanadium slag winnowing magnetic substances and leached tailing iron-rich aggregates.
In the invention, the coarse vanadium slag ball milling iron particles are iron ball milling media adopted in the ball milling process of large-particle-size vanadium slag obtained by transcribing and extracting vanadium by a ball mill; the refined vanadium slag winnowing magnetic material is a magnetic iron-containing material obtained by winnowing small-particle-size refined vanadium slag obtained after ball milling; the leaching tailings iron-rich aggregate is an iron-containing material obtained by screening leaching tailings.
In the invention, the waste iron material for extracting vanadium from vanadium slag contains metallic Fe and oxidation state Fe, and the mass ratio of the metallic Fe to the oxidation state Fe is 4-10: 1. Although the increase of the content of the iron in the oxidation state is beneficial to the heat release of the system, the consumption of the reducing agent aluminum is obviously increased after the proportion is too high.
Specifically, the mass ratio of metallic state Fe to oxidized state Fe may be 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, or 10: 1.
In the invention, the metallic state Fe is mainly iron simple substance/metallic iron; the Fe in the oxidized state is mainly iron oxide, such as Fe2O3,Fe3O4And FeO.
In the invention, the vanadium oxide is vanadium trioxide and/or vanadium pentoxide.
In the invention, TV in the vanadium trioxide is more than or equal to 63 weight percent, and TV in the vanadium pentoxide is more than or equal to 54 weight percent.
In a preferred aspect, the vanadium oxide is vanadium trioxide or a mixture of vanadium pentoxide and vanadium trioxide.
Further preferably, when the vanadium oxide is a mixture of vanadium pentoxide and vanadium trioxide, the mass ratio of the vanadium pentoxide to the vanadium trioxide is 2: 0.9-8. Specifically, the mass ratio of vanadium pentoxide to vanadium trioxide may be 2:0.9, 2:1, 2:2, 2:3, 2:4, 2:5, 2:6, 2:7, or 2: 8.
In the invention, the purity of the aluminum particles is more than or equal to 99 weight percent, and the granularity of the aluminum particles is 0.1-1 cm. Specifically, the particle size of the aluminum particles may be 0.1cm, 0.2cm, 0.3cm, 0.4cm, 0.5cm, 0.6cm, 0.7cm, 0.8cm, 0.9cm, or 1 cm.
In the invention, the actual addition amount of the aluminum particles is 0.9-1.1 times of the theoretical addition amount, wherein the theoretical addition amount is the theoretical aluminum consumption amount required by the oxides of the weak reducing metals (such as Fe, Mn, Ti and the like) and the non-metals (Si, C and the like) in the vanadium oxide in the ferrovanadium smelting mixture and the waste iron material after vanadium extraction from vanadium slag, and the required theoretical aluminum consumption amount is the sum of the corresponding stoichiometric coefficients of the corresponding weights of the weak reducing metals and the oxides in the smelting mixture in the thermite reduction reaction.
In the invention, the content of CaO in the lime is more than or equal to 80 weight percent, and the content of metal impurities in the lime is less than or equal to 1 weight percent. Specifically, the content of CaO in the lime may be 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%, or 99 wt%, and the content of metal impurities in the lime may be 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, or 1 wt%.
Wherein, the metal impurities in the lime comprise Al, Fe, Cu, Mn and the like.
In the invention, the specific smelting process comprises the following steps: and lowering the electrode to be in contact with the materials, electrifying to strike an arc, triggering a reaction, igniting and smelting, and continuously electrifying until smelting is finished after the ferrovanadium smelting mixture is completely melted to form a molten pool and no obvious crust is formed on the surface of the molten pool.
In the invention, the molten pool is a liquid mixture with certain fluidity formed by melting corundum slag and alloy together in the reaction process of a molten pool ferrovanadium smelting system or after the reaction is finished.
In the invention, the smelting method is one-step smelting or multi-stage smelting.
The one-step smelting is one-time raw material adding, the multi-stage method is multi-time feeding, and multiple deslagging operations can be carried out during the multi-stage method.
In the invention, after smelting is finished, a heat-insulating cover is added on the upper surface of the furnace body, then the furnace body is naturally cooled in the air, and then the furnace is disassembled to obtain the FeV50 alloy and smelting slag.
In the invention, after no obvious crust on the surface of the molten pool, the electric power is continuously electrified by unit alloy of 400-600kVA/t until the smelting is finished. Specifically, the electric power supply of the unit alloy (the alloy in the unit alloy refers to the prepared vanadium-titanium-aluminum alloy) can be 400kVA/t, 425kVA/t, 450kVA/t, 475kVA/t, 500kVA/t, 525kVA/t, 550kVA/t, 575kVA/t or 600 kVA/t.
Preferably, the vanadium content in the smelting slag is reduced by less than or equal to 0.05 weight percent/min at the end of smelting. Specifically, the vanadium content in the smelting slag can be reduced by 0.01 wt%/min, 0.02 wt%/min, 0.03 wt%/min, 0.04 wt%/min or 0.05 wt%/min.
The method disclosed by the invention uses the waste iron material obtained by extracting vanadium from the vanadium slag to replace or partially replace scrap iron or iron particles adopted in the traditional ferrovanadium alloy smelting process, and makes full use of the composition characteristics and cost advantages of the waste iron material obtained in the vanadium slag vanadium extraction process (the waste iron material contains a small amount of vanadium and contains iron as the main component, and if the waste iron material is treated as a process waste, the cost is relatively low, and if the waste iron material is used as a ferrovanadium alloy smelting raw material, the effect of main element iron in the waste iron material can be exerted, and the vanadium in the waste iron material can also be reduced into an alloy as a vanadium-containing raw material). By adopting the method, the main element iron in the vanadium-extracting waste iron material of the vanadium slag can be efficiently utilized, the vanadium in the vanadium-extracting waste iron material of the vanadium slag is fully extracted, the finally produced ferrovanadium alloy product is qualified in component and better in quality, the efficient comprehensive utilization of the vanadium-and iron-containing waste resources is realized, the production amount of production line process waste is reduced, and the production cost of ferrovanadium is reduced.
The present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.
The chemical composition of the FeV50 alloy products in the examples and comparative examples was measured by: GB/T8704.5 for V, GOST 14250.1-90 for Ti, GB/T8704.8 for Al, GB/T8704.6 for Si, and GB/T8704.9 for Mn. The method for measuring the chemical composition in the smelting slag comprises the following steps: the measurement was performed using an X-ray fluorescence analyzer (XRF).
Example 1
Vanadium pentoxide (55.0 wt% of TV), vanadium trioxide (64.0 wt% of TV), aluminum particles (the purity of the aluminum particles is 99.0 wt%, the particle size is 0.1cm, the actual addition amount of the aluminum particles is 1.0 time of the theoretical addition amount), vanadium slag vanadium extraction waste iron materials (the vanadium slag vanadium extraction waste iron materials are crude vanadium slag ball-milled iron particles, the mass ratio of metallic state Fe to oxidized state Fe in the vanadium slag vanadium extraction waste iron materials is 4:1) and lime (the content of CaO in lime is 85 wt%, and the content of metallic impurities is 1 wt%) are uniformly mixed to obtain a vanadium iron smelting mixture, then the vanadium iron smelting mixture is uniformly loaded into a smelting electric furnace for smelting, the electrode is lowered to be in contact with the materials, the arc is electrified, the reaction is triggered, the smelting is carried out (the smelting method is a one-step method), when the vanadium iron smelting mixture is completely melted to form a molten pool, the surface of the molten pool is not obviously crusted, continuously electrifying the unit alloy of 400kVA/t until the mass fraction reduction amplitude of vanadium in the smelting slag is 0.03%/min, adding a heat-insulating cover on the upper surface of a furnace body after smelting is finished, naturally cooling in the air, and then disassembling the furnace to obtain FeV50 alloy and smelting slag;
the chemical composition of the vanadium-extracting waste iron material of the vanadium slag is as follows: 80.0 wt% TFe, 2 wt% TV, 1.5 wt% Ti, 1 wt% Si, 1.2 wt% Mn;
the mass ratio of the vanadium pentoxide to the vanadium trioxide is 2:0.99, and the mass ratio of the vanadium pentoxide to the vanadium trioxide is 33:53:71: 15;
TV, TFe and Al in smelting slag2O3The mass fractions of the components are respectively 1.1 percent, 1.2 percent and 72.5 percent, and V, Al, Si and M in the FeV50 alloy productThe mass fractions of n and Ti are respectively 49.9%, 0.3%, 2.2%, 1.6% and 0.1%.
Example 2
Vanadium pentoxide (55.5 weight percent of TV), vanadium trioxide (66.0 weight percent of TV), aluminum particles (the purity of the aluminum particles is 99.5 weight percent, the granularity is 1cm, the actual addition amount of the aluminum particles is 1.1 times of the theoretical addition amount), vanadium slag vanadium extraction waste iron materials (the vanadium slag vanadium extraction waste iron materials are refined vanadium slag winnowing magnetic materials, the mass ratio of metallic state Fe to oxidation state Fe in the vanadium slag vanadium extraction waste iron materials is 6:1), scrap iron (the purity of the scrap iron is 99.5 weight percent, and the surface area of the scrap iron is 5 cm)2) Uniformly mixing the vanadium-iron smelting mixture with lime (the content of CaO in the lime is 90.0 wt%, and the content of metal impurities is 0.5 wt%) to obtain a vanadium-iron smelting mixture, then uniformly loading the vanadium-iron smelting mixture into an electric smelting furnace for smelting, lowering an electrode to be in contact with the material, electrifying for arc striking, triggering for reaction, carrying out ignition smelting (the smelting method is a multi-stage method), continuously electrifying by using unit alloy of 500kVA/t until the reduction range of the mass fraction of vanadium in the smelting slag is 0.05%/min after the vanadium-iron smelting mixture is completely melted to form a molten pool, and after no obvious crust exists on the surface of the molten pool, adding a heat-insulating cover on the upper surface of a furnace body after smelting is finished, naturally cooling in the air, and then removing the furnace to obtain a FeV50 alloy and smelting slag;
the chemical composition of the vanadium-extracting waste iron material of the vanadium slag is as follows: 90.0 wt% TFe, 1.5 wt% TV, 1 wt% Ti, 0.8 wt% Si, 0.5 wt% Mn;
the mass ratio of vanadium pentoxide to vanadium trioxide to aluminum particles to the vanadium slag vanadium extraction waste iron material to scrap iron to lime is 67:33:53:30:30:20, and the mass ratio of the vanadium slag vanadium extraction waste iron material to the scrap iron is 5: 5, the mass ratio of vanadium pentoxide to vanadium trioxide is 2: 0.99;
TV, TFe and Al in smelting slag2O3The mass fractions of V, Al, Si, Mn and Ti in the FeV50 alloy product are respectively 0.7%, 1.2% and 74.1%, and the mass fractions of V, Al, Si, Mn and Ti in the FeV50 alloy product are respectively 51.5%, 1.8%, 1.0%, 0.8% and 0.3%.
Example 3
Vanadium pentoxide (55.0 wt% of TV), vanadium trioxide (64.0 wt% of TV), aluminum particles (the purity of the aluminum particles is 99.0 wt%, the granularity is 0.5cm, the actual addition amount of the aluminum particles is 1.0 times of the theoretical addition amount), vanadium slag vanadium extraction waste iron materials (the vanadium slag vanadium extraction waste iron materials are leached tailings iron-rich aggregates, the mass ratio of metallic state Fe to oxidized state Fe in the vanadium slag vanadium extraction waste iron materials is 10:1) and lime (the content of CaO in lime is 85 wt%, and the content of metallic impurities is 0.6 wt%) are uniformly mixed to obtain a vanadium iron smelting mixture, then the vanadium iron smelting mixture is uniformly filled into a smelting electric furnace for smelting, an electrode is lowered to be in contact with the materials, electric arc striking is conducted, reaction is triggered, ignition smelting is carried out (the smelting method is a multi-stage method), the vanadium iron smelting mixture is completely melted to form a molten pool, and no obvious crust exists on the surface of the molten pool, continuously electrifying the unit alloy of 500kVA/t until the mass fraction reduction amplitude of vanadium in the smelting slag is 0.04%/min, adding a heat-insulating cover on the upper surface of a furnace body after smelting is finished, naturally cooling in the air, and then disassembling the furnace to obtain FeV50 alloy and smelting slag;
the chemical composition of the vanadium-extracting waste iron material of the vanadium slag is as follows: 80.0 wt% TFe, 3 wt% TV, 1.8 wt% Ti, 1.5 wt% Si, 1.2 wt% Mn;
the mass ratio of the vanadium pentoxide to the vanadium trioxide is (2: 8), the mass ratio of the vanadium pentoxide to the vanadium trioxide is (51: 75: 15), and the mass ratio of the vanadium pentoxide to the vanadium trioxide is (51: 75);
TV, TFe and Al in smelting slag2O3The mass fractions of V, Al, Si, Mn and Ti in the FeV50 alloy product are respectively 1.2%, 1.1% and 72.4%, and the mass fractions of V, Al, Si, Mn and Ti in the FeV50 alloy product are respectively 50.8%, 0.9%, 1.7%, 1.5% and 0.6%.
Example 4
Vanadium pentoxide (55.5 wt% of TV), vanadium trioxide (66.0 wt% of TV), aluminum particles (the purity of the aluminum particles is 99.5 wt%, the granularity is 0.8cm, the actual addition amount of the aluminum particles is 1.1 times of the theoretical addition amount), vanadium slag vanadium extraction waste iron materials (the vanadium slag vanadium extraction waste iron materials are a mixture of coarse vanadium slag ball-milling iron particles, fine vanadium slag winnowing magnetic materials and leaching tailing iron-rich aggregates, and the vanadium slag vanadium extraction waste vanadium iron materials are mixed to obtain the vanadium slag vanadium extraction waste iron-rich aggregateThe mass ratio of metallic state Fe to oxidation state Fe in the iron scrap is 7:1, and the iron filings (the purity of the iron filings is 99.5 wt%, and the surface area of the iron filings is 3cm2) Uniformly mixing the vanadium-iron smelting mixture with lime (the content of CaO in the lime is 90.0 wt%, and the content of metal impurities is 0.3 wt%) to obtain a vanadium-iron smelting mixture, then uniformly loading the vanadium-iron smelting mixture into an electric smelting furnace for smelting, lowering an electrode to be in contact with the material, electrifying for arc striking, triggering for reaction, carrying out ignition smelting (the smelting method is a one-step method), continuously electrifying by using unit alloy of 500kVA/t for electric power until the mass fraction reduction range of vanadium in the smelting slag is 0.02%/min after the vanadium-iron smelting mixture is completely melted to form a molten pool, and after no obvious crust exists on the surface of the molten pool, adding a heat preservation cover on the upper surface of a furnace body after smelting is finished, naturally cooling in the air, and then removing the furnace to obtain FeV50 alloy and smelting slag;
the chemical composition of the vanadium-extracting waste iron material of the vanadium slag is as follows: 90.0 wt% TFe, 1.5 wt% TV, 0.5 wt% Ti, 0.6 wt% Si, 0.4 wt% Mn;
the mass ratio of vanadium pentoxide to vanadium trioxide to aluminum particles to the vanadium slag vanadium extraction waste iron material to scrap iron to lime is 20:80:51:33:30:20, and the mass ratio of the vanadium slag vanadium extraction waste iron material to the scrap iron is 5: 4.5, the mass ratio of vanadium pentoxide to vanadium trioxide is 2: 8;
TV, TFe and Al in smelting slag2O3The mass fractions of V, Al, Si, Mn and Ti in the FeV50 alloy product are respectively 0.6%, 0.8% and 70.3%, and the mass fractions of V, Al, Si, Mn and Ti in the FeV50 alloy product are respectively 51.4%, 1.8%, 1.5%, 1.2% and 0.6%.
Example 5
Vanadium pentoxide (54 wt% of TV), vanadium trioxide (63 wt% of TV), aluminum particles (the purity of the aluminum particles is 99.5 wt%, the particle size is 0.5cm, the actual addition amount of the aluminum particles is 1.1 times of the theoretical addition amount), vanadium slag vanadium extraction waste iron materials (the vanadium slag vanadium extraction waste iron materials are a mixture of coarse vanadium slag ball-milling iron particles and refined vanadium slag winnowing magnetic substances, the mass ratio of metallic state Fe to oxidation state Fe in the vanadium slag vanadium extraction waste iron materials is 5:1), scrap iron (the purity of the scrap iron is 99.5 wt%, and the surface area of the scrap iron is 1 cm)2) Andlime (the content of CaO in the lime is 80.0 wt%, and the content of metal impurities is 0.3 wt%) is uniformly mixed to obtain a ferrovanadium smelting mixture, then the ferrovanadium smelting mixture is uniformly loaded into an electric smelting furnace for smelting, an electrode is lowered to be in contact with the materials, and is electrified for arc striking, a reaction is triggered, ignition smelting is carried out (the smelting method is a one-step method), after the ferrovanadium smelting mixture is completely melted to form a molten pool, after no obvious crust exists on the surface of the molten pool, electric power is continuously supplied by unit alloy of 600kVA/t until the reduction range of the mass fraction of vanadium in smelting slag is 0.02%/min, after the smelting is finished, a heat preservation cover is added on the upper surface of a furnace body, then the furnace is naturally cooled in the air, and then the furnace is disassembled to obtain FeV50 alloy and smelting slag;
the chemical composition of the vanadium-extracting waste iron material of the vanadium slag is as follows: 79 wt% TFe, 5 wt% TV, 1.2 wt% Ti, 1.3 wt% Si, 2 wt% Mn;
the mass ratio of vanadium pentoxide to vanadium trioxide to aluminum particles to the vanadium slag vanadium extraction waste iron material to scrap iron to lime is 20:80:51:25:40:20, and the mass ratio of the vanadium slag vanadium extraction waste iron material to the scrap iron is 5: 8, the mass ratio of vanadium pentoxide to vanadium trioxide is 2: 8;
TV, TFe and Al in smelting slag2O3The mass fractions of V, Al, Si, Mn and Ti in the FeV50 alloy product are respectively 0.5%, 0.7% and 72.1%, and the mass fractions of V, Al, Si, Mn and Ti in the FeV50 alloy product are respectively 51.5%, 1.5%, 1.3%, 1.0% and 0.5%.
Example 6
The process was carried out as described in example 1, except that the ferrovanadium mixture also contained iron filings having a purity of 99.5% by weight and a surface area of 5cm2The mass ratio of vanadium pentoxide to vanadium trioxide to aluminum particles to the waste iron materials from vanadium extraction of vanadium slag to iron filings to lime is 67:33:53:35:21:15, namely under the condition that the total iron amount in the furnace is not changed, the mass ratio of the waste iron materials from vanadium extraction of vanadium slag to iron filings is adjusted to 5:3, and FeV50 alloy and smelting slag are obtained;
TV, TFe and Al in smelting slag2O3The mass fractions of which are respectively 0.6 percent, 0.6 percent and 73.8 percent in the FeV50 alloy productThe mass fractions of V, Al, Si, Mn and Ti were 51.5%, 1.3%, 1.0%, 0.5% and 0.2%, respectively.
Comparative example 1
The FeV50 alloy is prepared by adopting the prior art, namely, the waste iron material for extracting vanadium from vanadium slag is not added, and the method comprises the following specific steps: mixing vanadium pentoxide (54 wt% of TV), vanadium trioxide (63 wt% of TV), aluminum particles (the purity of aluminum particles is 99.5 wt%, the particle size is 0.5cm, the actual addition amount of aluminum particles is 1 time of the theoretical addition amount), iron filings (the purity of iron filings is 99.5 wt%, and the surface area of iron filings is 1 cm)2) And lime (the content of CaO in the lime is 80.0 weight percent, and the content of metal impurities is 0.3 weight percent) are uniformly mixed according to the mass ratio of 80:20:49:64:15, then the mixture is put into a straight barrel furnace for ignition for self-propagating reaction, after the ferrovanadium smelting mixture is completely melted to form a molten pool, after no obvious crust is formed on the surface of the molten pool, the furnace body is electrified according to the power supply of 400kVA/t until the reduction range of the mass fraction of vanadium in the smelting slag is 0.02%/min, after the smelting is finished, the furnace body is transferred to a cooling zone for air cooling, and then the furnace is disassembled to obtain the FeV50 alloy and the smelting slag.
TV, TFe and Al in smelting slag2O3The mass fractions of V, Al, Si, Mn and Ti in the FeV50 alloy product are respectively 2.3%, 1.1% and 72.5%, and the mass fractions of V, Al, Si, Mn and Ti in the FeV50 alloy product are respectively 50.5%, 1.6%, 1.3%, 0.4% and 0.1%.
Comparative example 2
The method is implemented according to the embodiment 4, and is different from the method in that the mass ratio of vanadium pentoxide, vanadium trioxide, aluminum particles, vanadium slag vanadium extraction waste iron materials, scrap iron and lime is 20:80:45:18:16:20, and FeV50 alloy and smelting slag are obtained;
TV, TFe and Al in smelting slag2O3The mass fractions of V, Al, Si, Mn and Ti in the FeV50 alloy product are respectively 2.6%, 1.9% and 70.3%, and the mass fractions of V, Al, Si, Mn and Ti in the FeV50 alloy product are respectively 68.7%, 2.0%, 1.8%, 1.5% and 0.9%.
Test example 1
The vanadium smelting yield and the iron recovery rate in examples 1 to 6 and comparative examples 1 to 2 were measured, and the results are shown in Table 1.
Wherein the calculation formula of the vanadium smelting yield is as follows: the vanadium smelting yield is that the mass fraction of vanadium in the smelting slag is multiplied by the slag quantity, and the vanadium content of the raw material is multiplied by 100 percent;
the calculation formula of the iron recovery rate is as follows: the iron recovery rate is that the mass fraction of iron in the smelting slag is multiplied by the slag quantity, and the iron content in the vanadium extraction waste iron material of the vanadium slag is multiplied by 100 percent;
the calculation formula of the vanadium recovery rate is as follows: the recovery rate of vanadium is TV multiplied by theoretical slag increase in smelting slag and the vanadium content in vanadium extraction waste iron materials of vanadium slag is multiplied by 100 percent;
TABLE 1
The results in table 1 show that the method of the invention uses the waste iron materials obtained by vanadium extraction from vanadium slag to replace or partially replace scrap iron or iron particles adopted in the traditional ferrovanadium alloy smelting, fully utilizes the composition characteristics and cost advantages of the waste iron materials obtained in the vanadium extraction process from vanadium slag, finally produces ferrovanadium alloy products with qualified compositions, good quality, high vanadium smelting yield and low production cost, and can recover most of vanadium and iron in the waste iron materials compared with the conventional smelting.
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 preparing FeV50 alloy by using waste iron materials in vanadium extraction from vanadium slag is characterized by comprising the following steps: uniformly mixing vanadium oxide, aluminum particles, vanadium slag vanadium extraction waste iron materials, scrap iron and lime to obtain a ferrovanadium smelting mixture, uniformly loading the ferrovanadium smelting mixture into a smelting electric furnace for smelting, air-cooling a furnace body after smelting is finished, and then disassembling the furnace to obtain FeV50 alloy and smelting slag;
the chemical composition of the vanadium-extracting waste iron material of the vanadium slag is as follows: more than or equal to 79 weight percent of TFe, more than or equal to 1 weight percent of TV, less than or equal to 2 weight percent of Ti, less than or equal to 2 weight percent of Si, and less than or equal to 2 weight percent of Mn;
the mass ratio of the vanadium oxide to the aluminum particles to the waste iron materials for extracting vanadium from the vanadium slag to the scrap iron to the lime is 100:35-55:20-80:0-60: 10-20;
the mass ratio of the waste iron materials for extracting vanadium from the vanadium slag to the scrap iron is 5: 0-10.
2. The method according to claim 1, wherein the mass ratio of the iron waste materials for extracting vanadium from the vanadium slag to the iron filings is 5: 3-8.
3. The method as claimed in claim 1, wherein the waste iron material from vanadium slag vanadium extraction is at least one of coarse vanadium slag ball-milling iron particles, refined vanadium slag winnowing magnetic material and leached tailings iron-rich aggregate.
4. The method according to claim 1 or 3, characterized in that the mass ratio of metallic state Fe to oxidized state Fe in the waste iron material for extracting vanadium from vanadium slag is 4-10: 1.
5. The method according to claim 1, wherein the vanadium oxide is vanadium trioxide and/or vanadium pentoxide;
preferably, TV in the vanadium trioxide is more than or equal to 63 weight percent, and TV in the vanadium pentoxide is more than or equal to 54 weight percent;
preferably, the vanadium oxide is vanadium trioxide or a mixture of vanadium pentoxide and vanadium trioxide;
preferably, the mass ratio of the vanadium pentoxide to the vanadium trioxide is 2: 0.9-8.
6. The method of claim 1, wherein the aluminum particles have a purity of 99 wt.% or more and a particle size of 0.1 to 1 cm.
7. The method according to claim 1 or 2, wherein the purity of said iron pieces is not less than 99% by weight, and the surface area of said iron pieces is not more than 5cm2。
8. The method according to claim 1, wherein the content of CaO in the lime is not less than 80% by weight, and the content of metal impurities in the lime is not more than 1% by weight.
9. The method according to claim 1, wherein the specific process of smelting is as follows: lowering the electrode to contact with the materials, electrifying to strike an arc, triggering a reaction, carrying out ignition smelting, and continuously electrifying until smelting is finished after the ferrovanadium smelting mixture is completely melted to form a molten pool and no obvious crust is formed on the surface of the molten pool;
preferably, the vanadium content reduction range in the smelting slag is less than or equal to 0.05 weight percent/min as a standard after smelting.
10. The method as claimed in claim 9, wherein the unit alloy power supply during the continuous energization process is 400-600 kVA/t.
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| CN113913677A (en) * | 2021-09-29 | 2022-01-11 | 河钢承德钒钛新材料有限公司 | 50 ferrovanadium alloy and smelting method thereof |
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| CN115228623A (en) * | 2022-07-22 | 2022-10-25 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for simultaneously reducing P and Mn contents in ferrovanadium alloy |
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