CN108913894B - Self-stirring process for smelting ferrovanadium alloy - Google Patents
Self-stirring process for smelting ferrovanadium alloy Download PDFInfo
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Abstract
The invention discloses a self-stirring process for vanadium iron alloy smelting, belonging to the technical field of iron and steel smelting. The invention provides a ferrovanadium smelting self-stirring method which is simple to operate, long in furnace lining life and high in alloy yield. According to the method, after the aluminothermic reduction spontaneous reaction, a spherical self-stirring agent is added into a molten pool, the molten pool is fully stirred by means of self-stirring agent heat release, slag characteristic improvement, gas generation and the like, the deep reduction of materials is promoted, and after the primary self-stirring is finished, molten slag gold is poured into a casting sand mold for slag-gold mixed melting, so that the secondary self-stirring operation is realized. The method can obviously reduce the content of vanadium in the slag and greatly prolong the service life of the electric furnace by self-stirring operation in the ferrovanadium smelting process.
Description
Technical Field
The invention belongs to the technical field of iron and steel smelting, and particularly relates to a self-stirring process for vanadium iron alloy smelting.
Background
Ferrovanadium is the most widely used vanadium microalloyed master alloy in the steel industry. The vanadium-containing steel is widely applied to the industries of mechanical manufacturing, aerospace, road and bridge construction and the like, and the mechanical property of the steel is obviously improved due to the addition of vanadium. The industrialized ferrovanadium alloy is prepared by reducing vanadium-containing oxide and other vanadium-containing raw materials by using a reducing agent, and mutually dissolving the vanadium-containing oxide and other vanadium-containing raw materials in a solid solution state at a high temperature.
Most of the world's companies now adopt vanadium oxide (V)2O5/V2O3) The vanadium-iron alloy is taken as a raw material, a proper amount of reducing agent (Al/Si) and iron material are added to carry out thermal reduction reaction to produce the vanadium-iron alloy, and electric heating is assisted to ensure the heat requirement. The production process also comprises a straight cylinder furnace one-step process and a tilting furnace multi-stage process respectively, and finally alloy products with qualified quality can be obtained. The ferrovanadium alloy prepared by the thermal reduction method mainly utilizes the strong reducibility of a reducing agent to promote the reduction of vanadium oxide, thereby achieving the effect of poor slag.
CN102115821A provides a method for smelting ferrovanadium by a two-step method with metallic aluminum as a reducing agent, which comprises the steps of firstly reducing partial slag in the first smelting step, and then adding partial refining material into the primary alloy for refining to obtain a ferrovanadium alloy product. CN201510002957.4 provides a method for producing ferrovanadium by using a large-scale tilting furnace electro-aluminothermic process, adopts a technology combining multi-stage smelting and stepped aluminum distribution, and has the characteristics of convenient operation, aluminum consumption saving and ferrovanadium yield improvement. CN201710611520.X discloses a jet stirring system for a vanadium-titanium smelting furnace by an electro-aluminothermic process, which can assist smelting raw materials of a smelting pool to be effectively mixed. CN201710610957.1 discloses a smelting process for reducing vanadium residue in ferrovanadium smelting slag, which comprises the steps of adding corresponding smelting raw materials, completely forming a molten pool, spraying gas, and completing molten pool smelting under the condition of stirring.
From the technology disclosed above, the existing ferrovanadium alloy preparation mainly uses vanadium oxide as raw material, Al and Si (ferrosilicon) as reducing agent, and the ferrovanadium alloy is produced in an electric heating mode, and in order to improve the ferrovanadium smelting efficiency, the operation such as mechanical blowing is mainly adopted to realize the stirring of a molten pool; however, the methods may not have good slag-poor effect due to uneven stirring and blowing, and slag splashing is easily caused in the stirring process, so that the smelting time is prolonged, and the comprehensive yield and the smelting efficiency are reduced. The method of the invention adopts vanadium (V) flakes2O5) The vanadium-containing raw material is added with the self-stirring agent in the ferrovanadium smelting process, the metal aluminum is used as a reducing agent, the stirring of a smelting pool is promoted, the slag characteristics are improved, and the vanadium yield is improved and the service life of the smelting furnace is prolonged.
Disclosure of Invention
The invention provides a self-stirring process for smelting ferrovanadium alloy, which aims to solve the technical problems and comprises the following steps:
A. adding the mixture of vanadium flakes, aluminum particles, iron particles and lime into an electric furnace, igniting and carrying out self-heating reaction;
B. after the self-heating reaction is finished, adding a self-stirring agent, carrying out self-stirring operation of a molten pool, continuously supplying power, and maintaining the temperature of the system;
C. and then tipping the molten slag metal into a sand mold, and cooling to obtain a vanadium-iron alloy cake and low-vanadium smelting slag.
In the self-stirring process for smelting the ferrovanadium alloy, in the step A, the mass ratio of the vanadium flakes to the aluminum particles to the iron particles to the lime is 100: 50: 14-50: 5 to 15.
In the self-stirring process for smelting the ferrovanadium alloy, in the step A, the self-heating reaction time is 10-30 min.
In the self-stirring process for smelting the ferrovanadium alloy, in the step B, the self-stirring agent is prepared by the following method: mixing 1 part by mass of lime, 0-1 part by mass of calcium carbonate and 0-1.5 part by mass of ball-milled iron particles, and pelletizing and drying to obtain the finished product.
Preferably, in the self-stirring process for smelting ferrovanadium alloy, the mass ratio of lime, calcium carbonate and ball-milled iron particles in the self-stirring agent is 1: 0.5-1: 0 to 1.5.
In the self-stirring process for smelting the ferrovanadium alloy, in the step B, the diameter of the ball-milled iron particles is less than or equal to 3 mm.
In the self-stirring process for smelting the ferrovanadium alloy, in the step B, the particle size of the self-stirring agent is 5-20 mm, and the density is 3.0-5.0 kg/m3。
In the self-stirring process for smelting the ferrovanadium alloy, in the step B, the addition amount of the self-stirring agent is 5-15% of the mass of the vanadium flakes.
In the self-stirring process for smelting the ferrovanadium alloy, in the step B, the self-stirring agent is added in a pendulum type feeding mode, and the ratio of the feeding height to the slag layer height is controlled to be 1.5-2.5: 1.
in the self-stirring process for smelting the ferrovanadium alloy, in the step B, the continuous power supply time is 15-25 min.
In the self-stirring process for smelting the ferrovanadium alloy, in the step B, the system temperature is 1900-2100 ℃.
In the self-stirring process for smelting the ferrovanadium alloy, in the step C, the tilting angle of the molten slag metal in the sand mold is 30-45 degrees, and the ratio of the tilting height to the thickness of the slag metal is controlled to be 1-1.5: 1.
the invention has the beneficial effects that:
according to the method, the self-stirring agent is added in the smelting process, and the self-stirring agent is decomposed to release heat or decompose to generate a gas product, so that the flow of molten slag in a molten pool and the contact of slag-metal interfaces are promoted, the full stirring of the molten pool is realized, the deep reduction of materials is promoted, the optimization of the molten slag components of a smelting system is realized, the ratio of aluminum and magnesium in the molten slag is reduced, and the optimization of the characteristics of the molten slag, such as the melting point of the molten slag system, the viscosity of; then, in the process that the molten slag metal is tipped out of the furnace to a sand mold, the secondary self-stirring operation is realized because the slag metal is not mutually molten and has density difference. The vanadium content in the slag can be obviously reduced through the self-stirring operation in the ferrovanadium alloy smelting process, so that the purpose of reducing the vanadium loss in the slag is achieved, and the service life of the electric furnace is greatly prolonged.
Detailed Description
Specifically, the self-stirring process for smelting the ferrovanadium alloy comprises the following steps:
A. adding the mixture of vanadium flakes, aluminum particles, iron particles and lime into an electric furnace, igniting and carrying out self-heating reaction;
B. after the self-heating reaction is finished, adding a self-stirring agent, carrying out self-stirring operation of a molten pool, continuously supplying power, and maintaining the temperature of the system;
C. and then tipping the molten slag metal into a sand mold, and cooling to obtain a vanadium-iron alloy cake and low-vanadium smelting slag.
The process of the invention takes vanadium flakes as a vanadium-containing raw material and metal aluminum particles as a reducing agent, and adds the pelletized self-stirring agent into a smelting furnace in the smelting process to carry out slagging and molten pool self-stirring. When the electrode is heated and smelted, the first self-stirring operation is realized: by adding the self-stirring agent, on one hand, the self-stirring agent is decomposed and reacted after being added into a smelting system, and the self-stirring agent is used for decomposing and releasing heat or decomposing to generate gas products, so that the flow of molten slag in a molten pool and the contact of slag-metal interfaces are promoted, the molten pool is fully stirred, and the deep reduction of materials is promoted; on the other hand, the optimization of the slag components of the smelting system is realized, the proportion of aluminum and magnesium in the slag is reduced, and the optimization of the slag characteristics such as the melting point of the slag system, the viscosity of the slag and the like is realized.
After the electro-smelting is finished, the molten slag metal after the reaction is finished is tipped and discharged into a sand mold, so that the secondary self-stirring operation is realized: during the whole pouring process, obvious slag-metal mixing and melting occur due to the difference of gravitational potential energy and density of molten slag-metal, then secondary separation of the slag-metal is gradually realized in a sand mold, and the process is a strong stirring operation, so that the contact area of the slag-metal in the system is enlarged. And performing secondary self-stirring operation and cooling to obtain the ferrovanadium alloy and the low-vanadium smelting slag. The vanadium content in the slag can be obviously reduced through the self-stirring operation in the ferrovanadium alloy smelting process, so that the purpose of reducing the vanadium loss in the slag is achieved, and the service life of the electric furnace is greatly prolonged.
In the step A of the method, the mass ratio of the vanadium flakes to the aluminum particles to the iron particles to the lime in the mixture is 100: 50: 14-50: 5-15, and the granularity of each material is generally required to be less than or equal to 0.2 mm. After ignition, the system carries out self-heating reaction, the temperature in the self-heating reaction process is not required to be controlled, and the self-heating reaction is generally finished after 10-30 min.
The self-stirring agent used in the method is prepared by the following method: mixing 1 part by mass of lime, 0-1 part by mass of calcium carbonate and 0-1.5 part by mass of ball-milled iron particles, and pelletizing and drying to obtain the finished product.
Limestone in the self-stirring agent is mainly used for slagging, calcium carbonate can generate gas besides slagging, and the main purpose of ball milling of iron particles is to increase the density of material balls and improve the stirring strength after the addition of the material balls; the self-stirring agent is characterized in that limestone is used as a reference, calcium carbonate is gradually added, then ball-milling iron particles are added, and the effect is gradually increased; therefore, preferably, the mass ratio of the lime, the calcium carbonate and the ball-milled iron particles in the self-stirring agent is 1: 0.5-1: 0 to 1.5.
In order to achieve the optimal reaction kinetics effect, ensure that the density of the self-stirring agent is between that of the alloy and the molten slag, and realize the smooth addition and stirring effect of self-stirring, the particle size of the self-stirring agent is controlled to be 5-20 mm, and the density is controlled to be 3.0-5.0 kg/m3. The ball milling iron particles with the diameter less than or equal to 3mm are adopted, so that the particle size of the self-stirring agent is controlled and controlled when the ball is made.
In the self-stirring process for smelting the ferrovanadium alloy, in the step B, the addition amount of the self-stirring agent is 5-15% of the mass of the vanadium flakes.
In the step B of the method, the self-stirring agent is added in a pendulum type feeding mode, and the ratio of the feeding height to the slag layer height is controlled to be 1.5-2.5: 1, too low easily causes slow sinking speed of the self-stirring agent, and too high easily causes splashing of materials to the furnace wall in the adding process, thereby influencing the yield.
And in the step B, after the self-stirring agent is added, continuously supplying power for 15-25 min, and maintaining the system temperature at 1900-2100 ℃.
In the step C of the method, the tilting angle of the molten slag metal in the sand mold is 30-45 degrees, and the ratio of the tilting height to the slag metal thickness is controlled to be 1-1.5: 1, the proper tilting height and angle are favorable for the slag-metal mixing and melting in the process of casting the slag-iron and discharging, the splashing of the molten slag-metal is avoided, and the heat loss is reduced.
Preferably, the self-stirring process for vanadium iron alloy smelting comprises the following steps:
A. adding the mixture of the vanadium flakes, the aluminum particles, the iron particles and the lime into an electric furnace, igniting and carrying out self-heating reaction for 10-30 min; the mass ratio of the vanadium flakes to the aluminum particles to the iron particles to the lime is 100: 50: 14-50: 5-15;
B. after the self-heating reaction is finished, heating the electrode to 1900-2100 ℃, maintaining the temperature of the system, feeding electricity for a certain time, adding a self-stirring agent, performing self-stirring operation of a molten pool, and continuously feeding electricity for 15-25 min, wherein the temperature of the system is maintained at 1900-2100 ℃; the self-stirring agent has a particle size of 5-20 mm and a density of 3.0-5.0 kg/m3(ii) a The self-stirring agent is added in a pendulum type feeding mode, and the ratio of the feeding height to the slag layer height is controlled to be 1.5-2.5: 1; the self-stirring agent is prepared by the following method: mixing 1 part by mass of lime, 0.5-1 part by mass of calcium carbonate and 0-1.5 part by mass of ball-milled iron particles, and pelletizing and drying to obtain the calcium carbonate ball;
C. then, tipping the molten slag metal into a sand mold according to a tipping angle of 30-45 degrees, and controlling the ratio of the tipping height to the thickness of the slag metal to be 1-1.5: and 1, cooling to obtain a ferrovanadium alloy cake and low-vanadium smelting slag.
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Comparative example
100 parts of vanadium flakes, 50 parts of aluminum powder, 14 parts of iron powder and 10 parts of lime are mixed and placed in an electric furnace for ignition and arc striking, after the self-heating reaction is carried out for 30min, the system temperature is maintained at 2000 ℃ by electrifying, after 15min, the molten slag metal is tipped into a sand mold, and the vanadium-iron alloy cake and the smelting slag are obtained after cooling and separation. Al in the obtained smelting slag2O3The contents of MgO and CaO are 73%, 11% and 13% respectively, the content of vanadium in the slag is 1.9%, and the service life of the electric furnace is 180 furnace.
Example 1
Preparation of self-stirring agent: pelletizing and drying lime by a disc pelletizer, wherein the lime is obtained from a stirring agent and has an average particle size of 8mm and a density of 3.6kg/m3。
Smelting a ferrovanadium alloy: 100 parts by mass of vanadium flakes, 50 parts by mass of aluminum powder, 14 parts by mass of iron powder and 7 parts by mass of lime are mixed and placed in an electric furnace for ignition and arc striking, and after the self-heating reaction is carried out for 30min, the mixture is subjected to a pendulum feeder, wherein the ratio of the tilting height to the thickness of slag metal is 1.5: 1, adding 5 parts by mass of spherical self-stirring agent, promoting stirring of the slag metal and forming a low-melting-point slag system through sinking and melting of the material balls, continuously electrifying to keep the temperature of the system at about 2000 ℃, and after 15min, when the tilting angle is 30 degrees, the ratio of the tilting height to the thickness of the slag metal is 1: 1, tipping the molten slag metal into a sand mold, realizing slag metal mixing and secondary self-stirring operation in the casting and tipping process, and cooling to obtain a ferrovanadium cake and low-vanadium smelting slag.
Al in the obtained low-vanadium smelting slag2O3The contents of MgO and CaO are respectively 72%, 10% and 15%, the content of vanadium in the slag is 1.7%, and the service life of the electric furnace is 190.
Example 2
Preparation of self-stirring agent: lime and calcium carbonate are mixed according to the weight ratio of 1: 0.5 pelletizing and drying by means of a disk pelletizer, from a stirring agent, with an average particle diameter of 10mm and a density of 3.8kg/m3。
Smelting a ferrovanadium alloy: the method comprises the following steps of putting a mixture of 100 parts by mass of vanadium flakes, 50 parts by mass of aluminum powder, 14 parts by mass of iron powder and 5 parts by mass of lime into an electric furnace, igniting and striking an arc, carrying out self-heating reaction for 30min, and then feeding the mixture into a pendulum feeder, wherein the ratio of the tilting height to the slag metal thickness is 1.5: 1, adding 10 parts by mass of spherical self-stirring agent, through sinking and melting of the material balls, generating gas at the same time, promoting stirring of the slag metal and forming a low-melting-point slag system, continuously electrifying to keep the temperature of the system at about 2000 ℃, and after 15min, when the tilting angle is 45 degrees, the ratio of the tilting height to the thickness of the slag metal is 1.5: 1, tipping the molten slag metal into a sand mold, realizing slag metal mixing and secondary self-stirring operation in the casting and tipping process, and cooling to obtain a ferrovanadium cake and low-vanadium smelting slag.
Al in the obtained low-vanadium smelting slag2O3The contents of MgO and CaO are 71%, 9% and 17%, respectively, the content of vanadium in the slag is 1.4%, and the service life of the electric furnace is 265 furnace.
Example 3
Preparation of self-stirring agent: lime and calcium carbonate are mixed according to the weight ratio of 1: 1 pelletizing and drying by means of a disk pelletizer, from a stirring agent, with an average particle size of 10mm and a density of 4.0kg/m3。
Smelting a ferrovanadium alloy: the method comprises the following steps of putting a mixture of 100 parts by mass of vanadium flakes, 50 parts by mass of aluminum powder, 14 parts by mass of iron powder and 5 parts by mass of lime into an electric furnace, igniting and striking an arc, carrying out self-heating reaction for 30min, and then feeding the mixture into a pendulum feeder, wherein the ratio of the tilting height to the slag metal thickness is 1.5: 1, adding 10 parts by mass of spherical self-stirring agent, through sinking and melting of the material balls, generating gas at the same time, promoting stirring of the slag metal and forming a low-melting-point slag system, continuously electrifying to keep the temperature of the system at about 2000 ℃, and after 25min, when the tilting angle is 45 degrees, the ratio of the tilting height to the thickness of the slag metal is 1.5: 1, tipping the molten slag metal into a sand mold, realizing slag metal mixing and secondary self-stirring operation in the casting and tipping process, and cooling to obtain a ferrovanadium cake and low-vanadium smelting slag.
Al in the obtained low-vanadium smelting slag2O3The contents of MgO and CaO are respectively 70%, 8% and 18%, the content of vanadium in the slag is 1.3%, and the service life of the electric furnace is 282.
Example 4
Preparation of self-stirring agent: lime, calcium carbonate and ball-milled iron particles are mixed according to the weight ratio of 1: 1: 1 pelletizing and drying by means of a disk pelletizer, from a stirring agent, having an average particle diameter of 10mm and a density of4.2kg/m3。
Smelting a ferrovanadium alloy: 100 parts by mass of vanadium flakes, 50 parts by mass of aluminum powder, 10 parts by mass of iron powder and 5 parts by mass of lime are mixed and put into an electric furnace, ignition and arc striking are carried out, after 30min of self-heating reaction, the mixture is turned over by a pendulum feeder, and the ratio of the tilting height to the thickness of slag metal is 1.5: 1, adding 15 parts by mass of spherical self-stirring agent, through sinking and melting of the material balls, generating gas at the same time, promoting stirring of the slag metal and forming a low-melting-point slag system, continuously electrifying to keep the temperature of the system at about 2000 ℃, and after 20min, when the tilting angle is 30 degrees, the ratio of the tilting height to the thickness of the slag metal is 1: 1, tipping the molten slag metal into a sand mold, realizing slag metal mixing and secondary self-stirring operation in the casting and tipping process, and cooling to obtain a ferrovanadium cake and low-vanadium smelting slag.
Al in the obtained low-vanadium smelting slag2O3The contents of MgO and CaO are 71%, 8% and 18% respectively, the content of vanadium in the slag is 1.1%, and the service life of the electric furnace is 285.
Example 5
Preparation of self-stirring agent: lime, calcium carbonate and ball-milled iron particles are mixed according to the weight ratio of 1: 1: 1.5 pelletizing and drying by means of a disk pelletizer, from the stirrer, with an average particle diameter of 10mm and a density of 4.5kg/m3。
Smelting a ferrovanadium alloy: 100 parts by mass of vanadium flakes, 50 parts by mass of aluminum powder, 10 parts by mass of iron powder and 5 parts by mass of lime are mixed and put into an electric furnace, ignition and arc striking are carried out, after 30min of self-heating reaction, the mixture is turned over by a pendulum feeder, and the ratio of the tilting height to the thickness of slag metal is 1.5: 1, adding 15 parts by mass of spherical self-stirring agent, through sinking and melting of the material balls, generating gas at the same time, promoting stirring of the slag metal and forming a low-melting-point slag system, continuously electrifying to keep the temperature of the system at about 2000 ℃, and after 25min, when the tilting angle is 45 degrees, the ratio of the tilting height to the thickness of the slag metal is 1.5: 1, tipping the molten slag metal into a sand mold, realizing slag metal mixing and secondary self-stirring operation in the casting and tipping process, and cooling to obtain a ferrovanadium cake and low-vanadium smelting slag.
Al in the obtained low-vanadium smelting slag2O3MgO and CaO contents of 70%, 8% and 18%, respectively, vanadium content in slag of 1.0%, and electric powerThe furnace life was 296 furnaces.
Claims (6)
1. The self-stirring process for smelting the ferrovanadium alloy is characterized by comprising the following steps of: the method comprises the following steps:
A. adding the mixture of vanadium flakes, aluminum particles, iron particles and lime into an electric furnace, igniting and carrying out self-heating reaction;
B. after the self-heating reaction is finished, adding a self-stirring agent, carrying out self-stirring operation of a molten pool, continuously supplying power, and maintaining the temperature of the system; the self-stirring agent is prepared by the following method: mixing 1 part by mass of lime, 0.5-1 part by mass of calcium carbonate and 0-1.5 part by mass of ball-milled iron particles, and pelletizing and drying to obtain the calcium carbonate ball; wherein the diameter of the ball-milling iron particles is less than or equal to 3 mm; the self-stirring agent has a particle size of 5-20 mm and a density of 3.0-5.0 kg/m3；
C. Then tipping the molten slag metal into a sand mold, and cooling to obtain a vanadium-iron alloy cake and low-vanadium smelting slag; the tilting angle of the molten slag metal in the sand mold is 30-45 degrees, and the ratio of the tilting height to the thickness of the slag metal is controlled to be 1-1.5: 1.
2. the self-stirring process for vanadium iron alloy smelting according to claim 1, wherein: in the step A, the mass ratio of the vanadium flakes to the aluminum particles to the iron particles to the lime is 100: 50: 14-50: 5 to 15.
3. The self-stirring process for vanadium iron alloy smelting according to claim 1, wherein: in the step A, the self-heating reaction time is 10-30 min.
4. The self-stirring process for vanadium iron alloy smelting according to any one of claims 1 to 3, which is characterized in that: in the step B, the adding amount of the self-stirring agent is 5-15% of the mass of the vanadium flakes.
5. The self-stirring process for vanadium iron alloy smelting according to claim 1, wherein: in the step B, the self-stirring agent is added in a pendulum type feeding mode, and the ratio of the feeding height to the slag layer height is controlled to be 1.5-2.5: 1.
6. the self-stirring process for vanadium iron alloy smelting according to claim 1, wherein: in the step B, the continuous power supply time is 15-25 min; in the step B, the temperature of the system is 1900-2100 ℃.
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