CN108359769B - Method and device for deoxidizing and alloying silicon oxide-containing material - Google Patents
Method and device for deoxidizing and alloying silicon oxide-containing material Download PDFInfo
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- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
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Abstract
The invention relates to a method and a device for deoxidizing and alloying a material containing silicon oxide. After the converter finishes steelmaking, a proper amount of silicon oxide-containing material is added into the molten slag, the molten steel is taken as a cathode, a direct current electric field is applied between an inert anode and the cathode which are arranged in the molten slag to carry out the melting electrolytic reduction reaction of the silicon oxide, the silicon in the silicon oxide is reduced to enter the molten steel to achieve the aim of deoxidation alloying, and the oxygen in the silicon oxide is discharged to the atmosphere in the form of oxygen through the anodic reaction with the inert anode. The invention can melt, electrolyze and reduce the oxidized silicon, and can add a certain content of simple substance silicon to the molten steel while removing the excessive free oxygen in the molten steel. The device has simple structure and convenient operation, and the aim of deoxidation alloying with low cost and high efficiency can be fulfilled by utilizing the silicon oxide, thereby realizing CO2Zero emission, low carbon and environmental protection, and great social and economic benefits.
Description
Technical Field
The invention relates to the technical field of steel smelting, in particular to a method and a device for carrying out deoxidation alloying by using a silicon oxide-containing material.
Background
Deoxidation alloying is one of the basic tasks in steel making. In the basic oxygen furnace, oxygen is supplied from an oxygen lance to molten steel, and the molten steel at the end inevitably contains excess oxygen. The presence of oxygen in the steel, whether in a gaseous state, dissolved oxygen state, or in the form of oxides, reduces the quality of the steel. Therefore, after the smelting in the converter is completed, the molten steel must be subjected to a deoxidation alloying operation to remove excess oxygen from the molten steel. At present, most steel plants adopt a simple deoxidation alloying process, namely ferrosilicon, ferromanganese, aluminum ingots and the like are added into molten steel after the smelting of a converter is finished for deoxidation alloying, so that the yield of the alloy is low, the alloy consumption is high, and the steel-making cost is high. Under the current severe market situation, the internal excavation of enterprises becomes an important means for reducing loss. In terms of production process, how to achieve low-cost and high-efficiency production is a necessary condition for iron and steel enterprises to be in a neutral place in market competition. Therefore, how to reduce the deoxidation cost and realize economical steelmaking is a constant pursuit goal of steelmaking workers.
The unique mechanical and physicochemical properties of silicon make it a fundamental material for supporting the development of human society. Silicon dioxide is undoubtedly the most economical precursor for large-scale silicon production from a cost perspective, and thus current industrial production of silicon is based on carbothermic silicon dioxide, which generally requires very high temperatures to ensure rapid and complete reduction based on the relative chemical inertness of the oxide (the reaction temperature for producing silicon by carbothermic reduction is generally above l700 ℃). Such high reaction temperatures inevitably bring about a large amount of heat loss, and thus the carbothermic process for producing silicon is not energy efficient (about 30%). From the environmental and resource aspects, carbothermic processes consume large amounts of carbon-based materials, resulting in large forest destruction and large carbon emissions. Based on the total yield of metal silicon and ferrosilicon of about 1000 ten thousand t worldwide in 2009, carbon dioxide is discharged by about 6200 ten thousand t when silicon is prepared by carbothermic reduction; and consumes about 1000 million tons of charcoal, about 625 ten thousand hm of forest2。
Different from the traditional carbothermic method, the electrochemical metallurgy process adopts electrons as energy carriers, thereby effectively avoiding the introduction of impurities (carbon and other non-metals). More importantly, the electrons themselves are green energy carriers, with no additional carbon emissions. In human society, a large amount of electric energy infrastructures are available, and the installed capacity of electric energy from green renewable energy sources (solar energy, wind energy, geothermal energy, tidal energy, nuclear energy and the like) in a power grid is continuously increased, so that the electrochemical metallurgy process can be expected to be a more green semiconductor preparation method. The activity of electrons can be accurately and conveniently regulated and controlled by adjusting the potential of the electrode, so that theoretically all metals, semiconductors and alloys can be prepared by an electrochemical process. In the actual electrolytic process, the limit of electronic activity regulation is limited by the electrochemical window of the electrolyte. Traditional aqueous solutions have a narrow electrochemical window, and therefore only a few elements (such as nickel, cobalt, lead, zinc, etc.) can be prepared in aqueous solutions on a large scale. The inorganic molten salt is used as an ion conductor, has a wide electrochemical window and strong capability of dissolving compounds, and is an ideal electrolyte for electrochemical metallurgy. The advantages of molten salt electrochemical metallurgy are reflected in the great success of the electrolytic aluminum industry (adopting a molten salt electrodeposition method).
Containing SiO2The slag can be regarded as mixed molten salt, so that the introduction of an electrochemical method into the traditional smelting process is inspired, and a proper electric field is applied between the slag and a molten steel system, so that the SiO can be utilized2The green low-cost process for carrying out the molten steel deoxidation alloying can obviously reduce energy consumption, lighten environmental load, obviously reduce production cost and has good social and economic benefits.
The invention discloses a Chinese patent with publication number CN102653811A, namely a method for deoxidizing and alloying by using a ferro-silico-manganese alloy, and relates to a method for deoxidizing and alloying by using a ferro-silico-manganese alloy, which comprises the following steps: firstly, detecting the content of dissolved oxygen in a converter, taking the content of dissolved oxygen in the converter as the converter terminal point when the content of dissolved oxygen in the converter is blown to 600-1300 ppm, then adding the ferro-silico-manganese alloy into a steel ladle, stopping adding the ferro-silico-manganese alloy when the content of dissolved oxygen in the steel ladle reaches 100-300 ppm, inputting an aluminum wire into the steel ladle by using a wire feeder, and stopping inputting the aluminum wire when the content of dissolved oxygen in the steel ladle reaches 15-35 ppm, namely the smelting steel. The method utilizes the content of high dissolved oxygen to remove silicon contained in the silicon-manganese-iron alloy in the molten steel, namely, the ferrosilicon or the silicon alloy containing simple substance silicon is used for deoxidation alloying operation after steel making, and the technology has poor economical efficiency.
The invention discloses a Chinese patent 'silicomanganese high-efficiency absorbing alloy ball with the publication number of CN103131820A and a preparation method thereof', relating to a silicomanganese high-efficiency absorbing alloy ball, which is prepared by mixing silicomanganese alloy, ferrosilicon, manganese ore, high-alumina cement and a binder and preparing the mixture into alloy balls with the particle size of 20-50 mm. The silicon-manganese high-efficiency absorption alloy ball is added with a certain amount of high-alumina cement and a certain amount of binder besides silicon-manganese alloy, so that impurities are added to a smelting system in the steelmaking process, molten steel is polluted, and the application prospect is poor.
The invention discloses a Chinese patent with publication number CN103993124A 'a method for improving the yield of a semi-steel steelmaking Si alloy', and relates to a method for improving the yield of the semi-steel steelmaking Si alloy, which comprises the steps of adding a slagging material into a converter after adding semi-steel to perform converter smelting, then performing converter smelting end point control and tapping, and adding ferrosilicon to increase silicon in the semi-steel during tapping, and is characterized in that the slagging material comprises ferrosilicon, active lime and high-magnesium lime, the adding amount of the slagging material enables the slag alkalinity to be 3-4, and the adding amount of the ferrosilicon in the slagging material is 4-6 kg/ton of steel. By adopting the method provided by the invention, high-carbon-pulling tapping can be realized, and the end point oxygen activity is effectively reduced, so that the yield of the Si alloy is effectively improved. The silicon alloy method belongs to a conventional alloying method by using an alloy containing simple substance silicon, and has poor technical and economic benefits.
Disclosure of Invention
The invention aims to provide a method and a device for deoxidizing and alloying a silicon oxide-containing material, wherein the method is used for melting, electrolyzing and reducing silicon oxide by using an electric field to complete molten steel deoxidizing and alloying. Is a brand new green silicon deoxidation alloying technology. Realizing low-cost green production of CO2Zero emission, energy conservation and environmental protection, and great social and economic benefits.
In order to achieve the purpose, the invention adopts the following technical scheme:
the slag ion theory shows that the molten oxide is an electrolyte having ion conductivity, and contains anions or anion groups (such as oxygen ions and anion groups in which oxygen ions are associated), cations, and the like. The theoretical decomposition voltage value of the molten oxide can be measured by the potential of the corresponding primary cell, and can also be calculated by thermodynamic data. The principle is as follows: the electrical energy required for the decomposition of a compound is numerically equal to its free energy of formation at constant pressure, but of opposite sign, i.e.:
△GT θ＝-nFET θ
in the formula, ET θTheoretical decomposition voltage in standard state, V, F-Faraday constant, 96487C/mol electrons, n-number of electrons lost in reaction formula, △ GT θChange in standard free energy of reaction at constant pressure, J/mol. Calculated SiO2The decomposition voltage was 1.49V.
From the electrochemical principle, it is known that the electrolytic reduction reaction of the molten compound can be performed under a certain electrochemical reaction condition (by applying a direct current electric field or an electrode), and thus, the electric field force suitable for the decomposition of the molten silicon oxide can be selected to perform the electrolytic reduction reaction, as shown in the reaction formula (1).
Si4++4e＝Si(L)(1)
If the anode is selected to be an inert material, the anode does not participate in the electrolytic reaction to obtain O2And elemental Si is generated at the cathode interface, and the reaction formula of the electrolytic reduction process is as follows:
SiO2(L)＝Si(L)+O2(g)(2)
specifically, the following reaction can be decomposed:
Si4++4e＝Si(L)(cathode reaction)
2O2-＝O2(g)+4e (anodic reaction)
The invention utilizes the principle, and applies a stable direct current electric field between the anode arranged in the slag and the cathode arranged in the molten steel to ensure that the molten silicon oxide is subjected to electrolytic reduction reaction to produce simple substance silicon and oxygen, and the simple substance silicon is directly dissolved in the molten steel to achieve the aim of deoxidation and alloying.
A process for deoxidizing and alloying the silicon oxide-contained material includes such steps as adding the silicon oxide-contained material to molten slag, applying a DC electric field between the inertial anode in molten slag and the cathode in molten steel, electrochemical reaction to reduce silicon oxide, introducing the reduced silicon into molten steel, and discharging the oxygen in silicon oxide in the form of oxygen to atmosphere.
The method comprises the following steps:
1) controlling the tapping process: the converter slag-stopping and tapping, wherein lime and materials containing silicon oxide are added into molten steel in the tapping process, and the adding amount of the lime and the materials containing silicon oxide is determined according to the respective CaO and SiO in the two materials2Adding the contents of CaO and SiO after the two materials are added2In a weight ratio of CaO/SiO2The total amount of the added materials is controlled to be 5-20 Kg/ton of steel when the weight is 0.5-1.5.
2) Controlling the electrolytic reduction reaction: the steel ladle is transported to an electrolytic treatment station, an electrolytic reaction control device is utilized to apply an electric field to a molten slag and steel system for electrolytic reaction control, and the specific control process is as follows: firstly, placing an anode in molten slag in a steel ladle, and controlling the position of the anode in the molten slag to avoid contact with molten steel; placing the cathode in the molten steel; the anode is connected with the positive pole of a direct current power supply through a lead, the cathode is connected with the negative pole of the direct current power supply through a lead, and then a direct current electric field is applied to the anode and the cathode by the direct current power supply to carry out electrolytic reaction.
The voltage of the direct current power supply is controlled to be 1.5-5V, the output current I is 100-2000A, and 200A/m can be generated on a slag and anode reaction interface2～4000A/m2The current density.
The silicon oxide-containing material is SiO2A compound or mixture having a weight percent content of greater than 35% and a weight percent content of less than 50% CaO.
An electrolytic reaction control device adopted by a method for carrying out deoxidation alloying by using silicon oxide-containing materials comprises a direct current power supply control device, an anode lifting device, an anode, a cathode lifting device, a cathode and a steel ladle; an anode lifting device is arranged on one side of the steel ladle, an anode is arranged on the anode lifting device, and the anode is inserted into the molten slag in the steel ladle by the anode lifting device; the other side of the steel ladle is provided with a cathode lifting device, a cathode is arranged on the cathode lifting device, and the cathode is inserted into the molten steel in the steel ladle by the cathode lifting device; the anode and the cathode are connected with a direct current power supply control device through leads.
The cathode is of a composite structure with an inner layer and an outer layer, the outer layer is made of an insulating material resistant to high temperature and slag corrosion, the inner part is made of a high-temperature-resistant conductive material, and the cathode is cylindrical.
The anode is made of high-temperature-resistant metal ceramic or high-temperature-resistant metal and is cylindrical or flat, and the number of the anodes is more than one.
The outer layer of the cathode is made of high-temperature resistant ceramic or high-temperature resistant cement, and the inside of the cathode is made of graphite, metal ceramic or high-temperature resistant metal.
Compared with the prior art, the invention has the beneficial effects that:
a method and a device for deoxidizing and alloying materials containing silicon oxide, which use an electric field to melt, electrolyze and reduce the silicon oxide to complete the deoxidizing and alloying of molten steel. After the converter finishes steelmaking, a proper amount of silicon oxide-containing material is added into the molten slag, the molten steel is taken as a cathode, a direct current electric field is applied between an inert anode and the cathode which are arranged in the molten slag to carry out the melting electrolytic reduction reaction of the silicon oxide, the silicon in the silicon oxide is reduced to enter the molten steel to achieve the aim of deoxidation alloying, and the oxygen in the silicon oxide is discharged to the atmosphere in the form of oxygen through the anodic reaction with the inert anode.
The invention is applied to carry out the melting, electrolysis and reduction of silicon oxide to complete deoxidation alloying, and the technology can melt, electrolyze and reduce the silicon oxide, and can add a certain content of simple substance silicon to the molten steel while finishing removing the excessive free oxygen in the molten steel. Compared with other deoxidation alloying technologies and equipment, the device has simple structure and convenient operation, and the aim of deoxidation alloying with low cost and high efficiency can be fulfilled by utilizing silicon oxide, thereby being a brand new technologyThe low-cost green deoxidation alloying technology can realize CO2Zero emission, low carbon and environmental protection, and great social and economic benefits.
Drawings
FIG. 1 is a schematic view of the structure of an electrolytic reaction control apparatus according to the present invention.
In the figure: 1-anode lifting device, 2-anode, 3-slag, 4-molten steel, 5-steel ladle, 6-cathode lifting device, 7-cathode and 8-DC power supply control device.
Detailed Description
The following further describes embodiments of the present invention with reference to the accompanying drawings:
referring to fig. 1, a deoxidation alloying method using silicon oxide-containing material is disclosed, in which a suitable amount of silicon oxide-containing material is added to molten slag, a direct current electric field is applied between an inert anode placed in the molten slag and a cathode placed in molten steel to perform an electrochemical reaction, the silicon oxide is electrolytically reduced, the reduced silicon enters the molten steel, and oxygen in the silicon oxide is discharged into the atmosphere in the form of oxygen through an anodic reaction with the inert anode.
The method comprises the following steps:
1) controlling the tapping process: the converter slag-stopping and tapping, wherein lime and materials containing silicon oxide are added into molten steel in the tapping process, and the adding amount of the lime and the materials containing silicon oxide is determined according to the respective CaO and SiO in the two materials2Adding proper amount of CaO and SiO after the two materials are added2In a weight ratio of CaO/SiO20.5 to 1.5, if CaO/SiO in the silicon oxide-containing material2And (4) according with the requirements, lime does not need to be added, and the total amount of the added materials is controlled to be 5-20 Kg per ton of steel.
2) Controlling the electrolytic reduction reaction: the steel ladle is transported to an electrolytic treatment station, an electrolytic reaction control device is utilized to apply an electric field to a molten slag and steel system for electrolytic reaction control, and the specific control process is as follows: firstly, placing an anode 2 in molten slag 3 in a ladle, and controlling the position of the anode 2 in the molten slag 3 to avoid contact with molten steel 4; placing the cathode 7 in the molten steel 4; the anode 2 is connected with the positive pole of a direct current power supply through a lead, the cathode 7 is connected with the negative pole of the direct current power supply through a lead, and then a direct current electric field is applied to the anode 2 and the cathode 7 by the direct current power supply to carry out electrolytic reaction.
The voltage of the direct current power supply is controlled to be 1.5-5V, the output current I is 100-2000A, and 200A/m can be generated on a slag and anode reaction interface2～4000A/m2The current density.
The silicon oxide-containing material is SiO2A compound or mixture having a weight percent content of greater than 35% and a weight percent content of less than 50% CaO.
An electrolytic reaction control device adopted by a method for carrying out deoxidation alloying by using silicon oxide-containing materials comprises a direct current power supply control device 8, an anode lifting device 1, an anode 2, a cathode lifting device 6, a cathode 7 and a steel ladle 5; an anode lifting device 1 is arranged on one side of the steel ladle 5, an anode 2 is arranged on the anode lifting device 1, and the anode 2 is inserted into molten slag 3 in the steel ladle 5 by the anode lifting device 1; a cathode lifting device 6 is arranged on the other side of the steel ladle 5, a cathode 7 is arranged on the cathode lifting device 6, and the cathode 7 is inserted into the molten steel 4 in the steel ladle 5 by the cathode lifting device 6; the anode 2 and the cathode 7 are connected to a direct current power supply control device 8 through wires.
The cathode 7 is of a composite structure with an inner layer and an outer layer, the outer layer is made of an insulating material resistant to high temperature and slag corrosion, the inner part is made of a high-temperature-resistant conductive material, and the cathode 7 is cylindrical.
The anodes 2 are made of high-temperature resistant metal ceramics or high-temperature resistant metal and are cylindrical or flat plates, and the number of the anodes is more than one.
The outer layer of the cathode 7 is made of high-temperature resistant ceramic or high-temperature resistant cement, and the inside of the cathode 7 is made of graphite, metal ceramic or high-temperature resistant metal.
The output power of the DC power supply control device is 100KVA at most, the voltage can be 0-50V, and the output current is 0-2000A. The lime is the lime used in the conventional metallurgy.
Example 1:
referring to fig. 1, the electrolytic reaction control device includes an anode elevating device 1, an anode 2, a ladle 5, a cathode elevating device 6, a cathode 7, and a dc power supply control device 8. An anode lifting device 1 is arranged at the left side position above the steel ladle 5; the anode lifting device 1 is provided with 4 high-temperature-resistant metal molybdenum ceramic anodes 2, and the anodes 2 are inserted into the molten slag 3; the anode lifting device 1 can adjust the depth of the anode 2 inserted into the molten slag 3, and ensure that the anode 2 is contacted with the molten slag 3 but not contacted with the molten steel 4; a cathode lifting device 6 is arranged on the other side above the steel ladle 5, a cathode 7 is arranged on the cathode lifting device 6, the cathode 7 is a cylinder with an inner layer and an outer layer of composite structure, the outer layer is wrapped by high-temperature-resistant cement, and the inner part is a graphite rod; the cathode 7 is inserted into the molten steel 4; the cathode lifting device 6 can adjust the lifting stroke of the cathode 7, ensure that the cathode 7 passes through the slag 3 to be contacted with the molten steel 4 and can adjust the depth of the cathode 7 in the molten steel 4; the anode 2 and the cathode 7 are respectively connected to a positive electrode and a negative electrode on a direct current power supply control device 8 through leads.
The silica-containing material used in this example was river sand, the composition of which is shown in table 1;
TABLE 1 river sand main chemical composition wt%
The composition of the small lime particles used in this example is shown in Table 2.
TABLE 2 main chemical composition wt% of small particle lime
The anode is made of high-temperature-resistant metal molybdenum ceramic and is cylindrical, and the overall dimension of the anode is phi 300mm × 1000 mm;
the cathode is a cylinder with an inner layer and an outer layer of composite structure, the outer layer is wrapped by a high-temperature resistant cement protective layer with the thickness of 30mm, the inner part is made of high-purity graphite, the diameter phi is 200mm, and the overall size of the cathode is phi 260mm × 1500 mm.
The special electrolytic reaction control is applied to a 100t steel ladle for deoxidation alloying operation. The overall control process comprises the following steps: the weight of the converter molten steel is 102 tons, the smelting end point C content is 0.036 percent (weight percentage), the end point oxygen content is 0.071 percent (weight percentage), and the smelting is carried outThe final molten steel temperature is 1702 ℃; slag-blocking and tapping by a converter, adding small-particle lime and river sand into molten steel in the tapping process, wherein the adding amount of the small-particle lime is 10 Kg/ton of steel, the adding amount of the river sand is 10 Kg/ton of steel, and the total adding amount of materials is 20 Kg/ton of steel; CaO/SiO obtained by adding the two materials21.04 (weight percentage ratio).
And applying an electric field to the molten slag and steel system by using the electrolytic reaction control device to control the electrolytic reaction. Firstly, placing an anode 2 in molten slag 3 in a ladle 5, and controlling the position of the anode 2 in the molten slag 3 to avoid contacting with molten steel 4; placing the cathode 7 in the molten steel 4; the anode 2 is connected with the anode of a direct current power supply through a lead, the cathode 7 is connected with the cathode of the direct current power supply through a lead, then a direct current electric field is applied to the anode 2 and the cathode 7 by the direct current power supply to carry out electrolytic reaction, the voltage of the direct current power supply is controlled to be 5V, the output current I is 1800-2000A, and 3600-4000A/m can be generated on the reaction interface of the molten slag 3 and the anode 22The current density (the current density fluctuates within this range due to small variations in the electrode-slag contact interface due to slight surges of molten steel including slag during electrolysis). The effects of the embodiment are shown in Table 5.
Example 2:
the electrolytic reaction control device for this example was the same as in example 1.
The silica-containing material used in this example was wollastonite having the composition shown in Table 3;
TABLE 3 wollastonite in% by weight of the main chemical constituents
The special electrolytic reaction control is applied to a 100t steel ladle for deoxidation alloying operation. The overall control process comprises the following steps: the weight of the converter molten steel is 101 tons, the content of C at the smelting end point is 0.071 percent, the content of oxygen at the molten steel end point is 0.035 percent (weight percent), and the temperature of the molten steel at the smelting end point is 1697 ℃; slag stopping and tapping of the converter, and adding wollastonite into the molten steel in the tapping process; the adding amount of wollastonite is 8Kg per ton of steel; because of CaO/SiO in wollastonite2When the content is 0.9, no small-particle lime is needed to be added.
And applying an electric field to the molten slag and steel system by using the electrolytic reaction control device to control the electrolytic reaction. Firstly, placing an anode 2 in molten slag 3 in a ladle 5, and controlling the position of the anode 2 in the molten slag 3 to avoid contacting with molten steel 4; placing the cathode 7 in the molten steel 4; the anode 2 is connected with the anode of a direct current power supply through a lead, the cathode 7 is connected with the cathode of the direct current power supply through a lead, then a direct current electric field is applied to the anode 2 and the cathode 7 by the direct current power supply to carry out electrolytic reaction, the voltage of the direct current power supply is controlled to be 2.3V, the output current I is 800-1100A, and 1600-2200A/m can be generated on a slag and anode reaction interface2The current density (the current density fluctuates within this range due to small variations in the electrode-slag contact interface due to slight surges of molten steel including slag during electrolysis). The effects of the embodiment are shown in Table 5.
Example 3:
the electrolytic reaction control device for this example was the same as in example 1.
The silicon oxide-containing material used in this example was a high-melting slag having the composition shown in table 4;
TABLE 4 high-melting slag main chemical composition wt%
The special electrolytic reaction control is applied to a 100t steel ladle for deoxidation alloying operation. The overall control process comprises the following steps: the weight of the converter molten steel is 103 tons, the smelting end point C content is 0.064 percent, the molten steel end point oxygen content is 0.045 percent (weight percentage), and the smelting end point molten steel temperature is 1707 ℃; the converter blocks slag and taps, and high slag is added into the molten steel in the tapping process, and the adding amount is 15Kg per ton of steel; due to CaO/SiO in high-melting slag2If the requirement is met, no small-particle lime is needed to be added.
And applying an electric field to the molten slag and steel system by using the electrolytic reaction control device to control the electrolytic reaction. Firstly, placing an anode 2 in molten slag 3, and controlling the position of the anode 2 in the molten slag 3 to avoid contacting with molten steel 4; placing the cathode 7 in the molten steel 4; the anode 2 is connected with the positive pole of a direct current power supply through a lead, and the cathode 7 is connected with the DC power supply through a leadConnecting the negative electrodes of a DC power supply, applying a DC electric field to the anode 2 and the cathode 7 by the DC power supply for electrolytic reaction, controlling the voltage of the DC power supply at 3.8V, outputting the current I of 800-1000A, and generating 1600-2000A/m at the reaction interface of the molten slag 3 and the anode 22The current density (the current density fluctuates within this range due to small variations in the electrode-slag contact interface due to slight surges of molten steel including slag during electrolysis). The effects of the present invention are shown in Table 5
Example 4:
the electrolytic reaction control device for this example was the same as in example 1.
The silica containing material used in this example was river sand with the composition shown in table 1.
The special electrolytic reaction control is applied to a 100t steel ladle for deoxidation alloying operation. The overall control process comprises the following steps: 99 tons of converter molten steel, the content of C at the smelting end point of 0.085 percent, the content of oxygen at the molten steel end point of 0.030 percent (in percentage by weight), and the temperature of the molten steel at the smelting end point of 1685 ℃; slag-blocking and tapping by a converter, adding small-particle lime and river sand into molten steel in the tapping process, wherein the adding amount of the small-particle lime is 4 Kg/ton of steel, the adding amount of the river sand is 8 Kg/ton of steel, and the total adding amount of materials is 12 Kg/ton of steel; CaO/SiO obtained by adding the two materials20.52 (weight percentage ratio).
And applying an electric field to the molten slag and steel system by using the electrolytic reaction control device to control the electrolytic reaction. Firstly, placing an anode 2 in molten slag 3, and controlling the position of the anode 2 in the molten slag 3 to avoid contacting with molten steel 4; placing the cathode 7 in the molten steel 4; the anode 2 is connected with the anode of a direct current power supply through a lead, the cathode 7 is connected with the cathode of the direct current power supply through a lead, then a direct current electric field is applied to the anode 2 and the cathode 7 by the direct current power supply to carry out electrolytic reaction, the voltage of the direct current power supply is controlled to be 1.5V, the output current I is 300-500A, and 600-1000A/m can be generated on the reaction interface of the molten slag 3 and the anode 22The current density (the current density fluctuates within this range due to small variations in the electrode-slag contact interface due to slight surges of molten steel including slag during electrolysis). The effects of the present invention are shown in Table 5
Example 5:
the electrolytic reaction control device for this example was the same as in example 1.
The silica-containing materials used in this example were river sand and wollastonite, wherein the river sand composition is shown in Table 1 and the wollastonite composition is shown in Table 3.
The special electrolytic reaction control is applied to a 100t steel ladle for deoxidation alloying operation. The overall control process comprises the following steps: the weight of the converter molten steel is 105 tons, the smelting end point C content is 0.10 percent, the molten steel end point oxygen content is 0.023 percent (weight percent), and the smelting end point molten steel temperature is 1692 ℃; and (4) stopping slag and tapping of the converter, and adding river sand and wollastonite into the molten steel in the tapping process. The adding amount of the river sand is 1Kg per ton of steel; the adding amount of wollastonite is 4Kg per ton of steel, and the total adding amount of materials is 5Kg per ton of steel; CaO/SiO obtained by adding the two materials20.73 (weight percentage ratio).
And applying an electric field to the molten slag and steel system by using the electrolytic reaction control device to control the electrolytic reaction. Firstly, placing an anode 2 in molten slag 3, and controlling the position of the anode 2 in the molten slag 3 to avoid contacting with molten steel 4; placing the cathode 7 in the molten steel 4; the anode 2 is connected with the anode of a direct current power supply through a lead, the cathode 7 is connected with the cathode of the direct current power supply through a lead, then a direct current electric field is applied to the anode 2 and the cathode 7 by the direct current power supply to carry out electrolytic reaction, the voltage of the direct current power supply is controlled to be 1.8V, the output current I is 100-200A, and 200-400A/m can be generated on the reaction interface of the molten slag 3 and the anode 22The current density (the current density fluctuates within this range due to small variations in the electrode-slag contact interface due to slight surges of molten steel including slag during electrolysis). The effects of the embodiment are shown in Table 5.
Example 6:
the electrolytic reaction control device for this example was the same as in example 1.
The silica-containing material used in this example was a high-melting slag having the composition shown in Table 4.
The special electrolytic reaction control is applied to a 100t steel ladle for deoxidation alloying operation. The overall control process comprises the following steps: 106 tons of converter molten steel, 0.041 percent of smelting end point C, 0.069 percent of molten steel end point oxygen (weight percentage), and smelting end pointThe temperature of the molten steel is 1712 ℃; the converter blocks slag and taps, high slag and small-sized lime are added into the molten steel in the tapping process, the adding amount of the high slag is 8.5 Kg/ton of steel, and the adding amount of the small-sized lime is 1.5 Kg/ton of steel; adding 10Kg of materials per ton of steel; CaO/SiO obtained by adding the two materials21.50 (weight percentage ratio).
And applying an electric field to the molten slag and steel system by using the electrolytic reaction control device to control the electrolytic reaction. Firstly, placing an anode 2 in molten slag 3, and controlling the position of the anode 2 in the molten slag 3 to avoid contacting with molten steel 4; placing the cathode 7 in the molten steel 4; the anode 2 is connected with the anode of a direct current power supply through a lead, the cathode 7 is connected with the cathode of the direct current power supply through a lead, then a direct current electric field is applied to the anode 2 and the cathode 7 by the direct current power supply to carry out electrolytic reaction, the voltage of the direct current power supply is controlled to be 4.2V, the output current I is 1300-1500A, and 2600-3000A/m can be generated on the reaction interface of the molten slag 3 and the anode 22The current density (the current density fluctuates within this range due to small variations in the electrode-slag contact interface due to slight surges of molten steel including slag during electrolysis). The effects of the present invention are shown in Table 5
TABLE 5 melting electrolytic deoxidation alloying effect of silicon oxide-containing slag
Claims (2)
1. A method for deoxidizing and alloying materials containing silicon oxide is characterized in that the materials containing silicon oxide are added into slag, a direct current electric field is applied between an inert anode placed in the slag and a cathode placed in molten steel to carry out electrochemical reaction, the silicon oxide is subjected to electrolytic reduction, the reduced silicon enters the molten steel, and oxygen in the silicon oxide is discharged into the atmosphere in the form of oxygen through the anodic reaction with the inert anode; adding lime and materials containing silicon oxide into molten steel in the tapping process, wherein the adding amount of the lime and the materials containing silicon oxide is respectively CaO and SiO in the two materials2Adding the contents of CaO and SiO after the two materials are added2Is CaO-SiO2The total amount of the added materials is controlled to be 5-20 Kg/ton of steel;
the method comprises the following steps:
1) controlling the tapping process: the converter slag-stopping and tapping, wherein lime and materials containing silicon oxide are added into molten steel in the tapping process, and the adding amount of the lime and the materials containing silicon oxide is determined according to the respective CaO and SiO in the two materials2Adding the contents of CaO and SiO after the two materials are added2In a weight ratio of CaO/SiO2The total amount of the added materials is controlled to be 5-20 Kg/ton of steel;
2) controlling the electrolytic reduction reaction: the steel ladle is transported to an electrolytic treatment station, an electrolytic reaction control device is utilized to apply an electric field to a molten slag and steel system for electrolytic reaction control, and the specific control process is as follows: firstly, placing an anode in molten slag in a steel ladle, and controlling the position of the anode in the molten slag to avoid contact with molten steel; placing the cathode in the molten steel; the anode is connected with the positive pole of a direct current power supply through a lead, the cathode is connected with the negative pole of the direct current power supply through a lead, and then a direct current electric field is applied to the anode and the cathode by the direct current power supply to carry out an electrolytic reaction;
the silicon oxide-containing material is SiO2A compound or mixture having a weight percent content of greater than 35% and a weight percent content of less than 50% CaO.
2. The method as claimed in claim 1, wherein the DC power supply voltage is controlled to be 1.5-5V, the output current I is 100-2000A, and 200A/m can be generated at the interface of the slag and the anode reaction2～4000A/m2The current density.
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| CN102912081A (en) * | 2012-10-23 | 2013-02-06 | 鞍钢股份有限公司 | Method for processing molten steel and improving cleanliness of steel by aid of external electric field |
| CN104975132A (en) * | 2014-04-10 | 2015-10-14 | 鞍钢股份有限公司 | Method of reducing oxidability of furnace slag with application of electric field |
| CN203807569U (en) * | 2014-04-11 | 2014-09-03 | 鞍钢股份有限公司 | Electrolytic reaction control device for degrading slag oxidability |
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