CN110846468A - Method for smelting vanadium-containing alloy steel by replacing vanadium alloy with vanadium pentoxide - Google Patents
Method for smelting vanadium-containing alloy steel by replacing vanadium alloy with vanadium pentoxide Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- 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
- C21C7/0006—Adding metallic additives
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- C—CHEMISTRY; METALLURGY
- 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
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/06—Deoxidising, e.g. killing
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- C—CHEMISTRY; METALLURGY
- 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
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/072—Treatment with gases
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- C—CHEMISTRY; METALLURGY
- 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
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/076—Use of slags or fluxes as treating agents
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Abstract
The invention provides a method for smelting vanadium-containing alloy steel by using vanadium pentoxide to replace vanadium alloy, which comprises the following steps: adding a mixture of flaky vanadium pentoxide and aluminum into the deoxidized molten steel, blowing argon to the bottom of the steel ladle after alloying, refining and continuously casting to obtain the vanadium-containing alloy steel. Compared with the traditional technology, the method has the advantages that the total yield of vanadium is improved by about 15%, the overall process is energy-saving, the material-saving effect is obvious, the development directions of energy conservation, consumption reduction and low carbon circulation in the steel industry are met, and the method has important significance in promoting the high-efficiency utilization of vanadium resources and the development of vanadium microalloying steelmaking technology in China.
Description
Technical Field
The invention belongs to the field of alloy steel preparation, relates to a preparation method of vanadium-containing alloy, and particularly relates to a method for smelting vanadium-containing alloy steel by using vanadium pentoxide instead of vanadium alloy.
Background
Vanadium is an important alloy element in steel production and is called metal vitamin. The addition of vanadium to steel can significantly improve the properties of the steel. Practice shows that 0.1% of vanadium is added into the structural steel, so that the strength can be improved by 10-20%, the structural weight is reduced by 15-25%, and the cost is reduced by 8-10%. If the vanadium-containing high-strength steel is adopted, the weight of the metal structure can be reduced by 40-50%, and the cost is reduced by 15-30% compared with that of the common structural steel. In recent years, the yield of Chinese vanadium-containing steel is continuously improved, the variety is continuously increased, and the development is very rapid particularly in the aspects of construction steel, pipeline steel, heavy rail steel, automobile and train structural steel and the like.
At present, when a converter smelts general vanadium-containing steel, a vanadium alloying process is mostly carried out by adopting ferrovanadium, but a large amount of raw materials, excellent reducing agents such as silicon and aluminum and a large amount of electric quantity are consumed in the ferrovanadium smelting process, and a large amount of smoke is generated to pollute the environment. Influenced by process and equipment, feedstock V2O5The vanadium in the vanadium can not completely enter the ferrovanadium, so that the resource utilization rate and the yield of alloy elements are not high.
Vanadium-nitrogen alloy, vanadium wire, vanadium rod and other vanadium-containing alloys are also used for alloying, but ferrovanadium is cheaper, so ferrovanadium is generally adopted for refining, but the materials are easy to splash during refining by the method, the waste and pollution are serious, the energy consumption is increased, the service life of the converter is reduced, and the smelting cost is improved; in the production process of ferrovanadium, the technological process is mainly to make the flaky V2O5And smelting the pig iron by using an electrode or other heating methods to obtain ferrovanadium, adding the calculated ferrovanadium amount into a steel ladle when the converter discharges steel 1/3-1/2, melting the ferrovanadium by physical heat of molten steel, and melting the vanadium into the molten steel to realize alloying, wherein the whole process is basically a physical process, and finally the vanadium enters the steel. The process consumes much energy, not only has high processing cost, but also has serious pollution. The alloying principle of vanadium-containing alloys such as vanadium-nitrogen alloy, vanadium wire and vanadium rod is basically the same as that of ferrovanadium.
CN 105369113A discloses a process for smelting vanadium-containing molten steel by direct alloying of calcium vanadate, which comprises the following steps: a, adding a calcium vanadate raw material into smelting molten steel, adding a first batch of reducing agent, and reacting for 5-8 min; b, adding a second batch of reducing agent into the molten steel, and reacting for more than 5 min; c, after the vanadium element in the molten steel is stable, adding vanadium-containing alloy to adjust the vanadium content in the molten steel to a target value. The method firstly adds calcium vanadate and then adds a reducing agent, so that the reduction reaction has poor stability and the phenomenon of incomplete reduction of high-valence vanadium is easy to occur.
The process for realizing vanadium steel alloying generally has high energy consumption and serious pollution, and particularly needs to be improved at present when energy conservation and emission reduction are advocated and consumption and environmental pollution are reduced, so that the invention analyzes and experiments various processes by research, and uses the sheet V2O5The process method is directly used in converter steelmaking to realize vanadium steel alloying.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for smelting vanadium-containing alloy steel by using vanadium pentoxide to replace vanadium alloy, the total yield of vanadium (vanadium resource utilization rate) in the method is improved by about 15% compared with the traditional technology, the overall process is energy-saving, the material-saving effect is obvious, the method accords with the development directions of energy conservation, consumption reduction and circulating low carbon in the steel industry, and has important significance for promoting the high-efficiency utilization of vanadium resources and the development of vanadium microalloying steelmaking technology in China.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for smelting vanadium-containing alloy steel by using vanadium pentoxide to replace vanadium alloy, which comprises the following steps:
adding a mixture of flaky vanadium pentoxide and aluminum into the deoxidized molten steel, blowing argon to the bottom of the steel ladle after alloying, refining and continuously casting to obtain the vanadium-containing alloy steel.
In the invention, the alloy can be added into the molten steel to regulate and control the performance of the steel according to the performance requirement of the cast steel after oxygen removal.
In the invention, Al and V are generated in the process of producing the vanadium-containing steel grade2O5In the ladle, explosive reaction occursIt is described that the reaction temperature in the closed vessel is up to 3000 ℃ or higher, and V is ensured to avoid the violent reaction2O5So that a mixture of flaky vanadium pentoxide and aluminum is added to the molten steel.
In a preferred embodiment of the present invention, the mass ratio of the flaky vanadium pentoxide to the aluminum is 1:0.4 to 0.6, for example, 1:0.42, 1:0.45, 1:0.48, 1:0.5, 1:0.52, 1:0.55 or 1:0.58, but the present invention is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable, and 1:0.5 is preferable.
In the invention, the adding proportion of aluminum is the guarantee for ensuring the complete reduction of the flaky vanadium pentoxide. The cost is increased due to excessive addition of aluminum; the addition amount is too small, and the reduction of the flaky vanadium pentoxide is insufficient. Through multiple experimental summaries, the applicable ratio of the mass ratio of the flaky vanadium pentoxide to the aluminum is 1: 0.4-0.6, and the optimal ratio is 1: 0.5. The vanadium content and other alloy component requirements required by smelting steel species are ensured.
As a preferable technical scheme of the invention, the refining slag and the lime are added into the molten steel before the deoxidation.
In a preferred embodiment of the present invention, the amount of the refining slag is 0.2 to 0.3% by mass of the molten steel, for example, 0.21%, 0.22%, 0.23%, 0.24%, 0.25%, 0.26%, 0.27%, 0.28%, or 0.29%, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
Preferably, the lime is added in an amount of 0.2 to 0.3% by mass of the molten steel, such as 0.21%, 0.22%, 0.23%, 0.24%, 0.25%, 0.26%, 0.27%, 0.28%, or 0.29%, but not limited to the above-mentioned values, and other values not listed in the above-mentioned numerical range are also applicable.
In a preferred embodiment of the present invention, the deoxidizing agent used in the deoxidation is aluminum.
In a preferred embodiment of the present invention, the amount of the deoxidizer is 0.1 to 0.3%, for example, 0.12%, 0.15%, 0.18%, 0.2%, 0.22%, 0.25%, or 0.28% by mass of the molten steel, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
As a preferable technical scheme of the invention, the oxygen content in the deoxidized molten steel is not more than 40 ppm.
In the invention, in the process of putting steel in the converter, a pure aluminum ingot is used as a deoxidizer to perform strong deoxidation treatment on molten steel, the addition amount and the addition time of the aluminum ingot are controlled to ensure the deoxidation effect of the molten steel, and conditions are created for ensuring the stable reduction of vanadium pentoxide. The converter adopts one-time deep deoxidation, and the oxygen content is lower than 40 ppm.
In a preferred embodiment of the present invention, the argon blowing time is 2 to 3min, such as 2.1min, 2.2min, 2.3min, 2.4min, 2.5min, 2.6min, 2.7min, 2.8min, or 2.9min, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are also applicable.
Preferably, the argon blowing strength is 0.23 to 0.45MPa, such as 0.25MPa, 0.28MPa, 0.30MPa, 0.32MPa, 0.35MPa, 0.38MPa, 0.40MPa or 0.42MPa, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
In the invention, the ladle bottom argon blowing can promote the floating of the inclusion. The stirred molten steel promotes the non-metallic inclusion in the steel to collide and grow, the floating argon bubbles can absorb gas in the steel, and the inclusion suspended in the molten steel is adhered to the surface of the molten steel and is absorbed by a slag layer. Stirring with argon blowing simultaneously on V2O5The kinetic conditions of the reduction are also of critical importance. The argon blowing process plays an important role in homogenizing components, homogenizing temperature, accelerating mass transfer, enhancing heat transfer, improving the castability of molten steel, removing impurities and gases, improving the atmosphere in a refining furnace and the like, so the argon blowing time and the argon blowing intensity must be reasonably controlled.
In the invention, in the process of producing the steel grade containing vanadium, the aluminum and the vanadium pentoxide generate explosive oxidation reaction in the steel ladle to release heat, and in order to prevent splashing accidents, prevent the volatilization of vanadium sheets and reduce the yield, the adding time needs to be researched. After the addition of deoxidant and lime during tapping, the calculated addition is completedAmount of sheet V2O5And mixtures of aluminum. Can promote and guarantee V2O5The vanadium content and other alloy components required by smelting steel species are achieved through stable reduction.
As a preferred technical scheme of the invention, the method for smelting vanadium-containing alloy steel by using vanadium pentoxide to replace vanadium alloy comprises the following steps:
adding 0.2-0.3% of refining slag and 0.2-0.3% of lime by mass of molten steel into the molten steel, adding 0.1-0.3% of aluminum by mass of the molten steel for deoxidation, adding a mixture of flaky vanadium pentoxide and aluminum into the deoxidized molten steel, wherein the mass ratio of the flaky vanadium pentoxide to the aluminum is 1: 0.4-0.6, blowing argon to the bottom of the steel ladle for not less than 5min after alloying, and refining and continuously casting to obtain the vanadium-containing alloy steel.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the invention provides a method for smelting vanadium-containing alloy steel by replacing vanadium alloy with vanadium pentoxide, which is used for successfully smelting the vanadium-containing alloy steel by replacing the vanadium alloy with flaky vanadium pentoxide in a converter and is applied to the production of smelting the vanadium-containing steel, so that the utilization rate of vanadium resources is effectively improved, and the conversion of vanadium steel alloying smelting modes is promoted;
(2) the invention provides a method for smelting vanadium-containing alloy steel by using vanadium pentoxide to replace vanadium alloy, which solves the problem of unstable vanadium yield of vanadium-containing steel prepared by directly alloying vanadium flakes;
(3) the invention provides a method for smelting vanadium-containing alloy steel by using vanadium pentoxide to replace vanadium alloy, which improves the comprehensive recovery rate of vanadium, and the comprehensive recovery rate of vanadium is improved by about 15 percent compared with the alloying process of a sheet vanadium-vanadium alloy-converter;
(4) the invention provides a method for smelting vanadium-containing alloy steel by using vanadium pentoxide to replace vanadium alloy, wherein the reduction rate of vanadium in the method reaches 98.33%, and the fluctuation is less than 3%;
(5) the invention provides a method for smelting vanadium-containing alloy steel by using vanadium pentoxide instead of vanadium alloy, which is suitable for producing all vanadium-containing microalloy steel.
Drawings
FIG. 1 is a schematic process flow diagram of a method for smelting vanadium-containing alloy steel by using vanadium pentoxide to replace vanadium alloy.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
The embodiment provides a method for smelting vanadium-containing alloy steel by using vanadium pentoxide instead of vanadium alloy, which comprises the following steps:
adding 200kg of refining slag and 200kg of lime into 70t of molten steel, adding 150kg of aluminum for deoxidation, adding a mixture of flaky vanadium pentoxide and aluminum into the deoxidized molten steel, wherein the mass ratio of the flaky vanadium pentoxide to the aluminum is 1:0.5, blowing argon to the bottom of a steel ladle for 2.5min after alloying, and the argon blowing strength is 0.35MPa, and refining and continuously casting to obtain the vanadium-containing alloy steel.
Example 2
The method for smelting vanadium-containing alloy steel by using vanadium pentoxide to replace vanadium alloy is the same as that in example 1 except that the mass ratio of the flaky vanadium pentoxide to aluminum is 1: 0.4.
Example 3
The method for smelting vanadium-containing alloy steel by using vanadium pentoxide to replace vanadium alloy is the same as that in example 1 except that the mass ratio of the flaky vanadium pentoxide to aluminum is 1: 0.6.
Example 4
The embodiment provides a method for smelting vanadium-containing alloy steel by using vanadium pentoxide instead of vanadium alloy, which comprises the following steps:
adding 140kg of refining slag and 140kg of lime into 70t of molten steel, adding 70kg of aluminum for deoxidation, adding a mixture of flaky vanadium pentoxide and aluminum into the deoxidized molten steel, wherein the mass ratio of the flaky vanadium pentoxide to the aluminum is 1:0.4, blowing argon to the bottom of a steel ladle for 2min after alloying, and the argon blowing strength is 0.45MPa, and refining and continuously casting to obtain the vanadium-containing alloy steel.
Example 5
The embodiment provides a method for smelting vanadium-containing alloy steel by using vanadium pentoxide instead of vanadium alloy, which comprises the following steps:
adding 210kg of refining slag and 210kg of lime into 70t of molten steel, adding 200kg of aluminum for deoxidation, adding a mixture of flaky vanadium pentoxide and aluminum into the deoxidized molten steel, wherein the mass ratio of the flaky vanadium pentoxide to the aluminum is 1:0.6, blowing argon to the bottom of a steel ladle for 3min after alloying, and the argon blowing strength is 0.23MPa, and refining and continuously casting to obtain the vanadium-containing alloy steel.
Example 6
The embodiment provides a method for smelting vanadium-containing alloy steel by using vanadium pentoxide instead of vanadium alloy, which comprises the following steps:
adding 180kg of refining slag and 180kg of lime into 70t of molten steel, adding 180kg of aluminum for deoxidation, adding a mixture of flaky vanadium pentoxide and aluminum into the deoxidized molten steel, wherein the mass ratio of the flaky vanadium pentoxide to the aluminum is 1:0.5, blowing argon to the bottom of a steel ladle for 2.5min after alloying, and the argon blowing strength is 0.30MPa, and refining and continuously casting to obtain the vanadium-containing alloy steel.
Comparative example 1
The comparative example provides a method for smelting vanadium-containing alloy steel by using vanadium pentoxide instead of vanadium alloy, and the method is the same as that in example 1 except that the added vanadium pentoxide is massive vanadium pentoxide, and other conditions are the same.
Comparative example 2
The method is the same as the embodiment 1 except that the flaky vanadium pentoxide and the reducing agent aluminum are added in sequence according to the proportion in the embodiment 1.
Comparative example 3
The comparative example provides a method for smelting vanadium-containing alloy steel by using vanadium pentoxide instead of vanadium alloy, and the method is the same as the method in the example 1 except that the time for blowing argon to the bottom of a steel ladle is 5 min.
The vanadium total yield (vanadium resource utilization) and the vanadium reduction ratio of the vanadium-containing alloys of examples 1 to 6 and comparative examples 1 to 3 were measured, and the results are shown in table 1.
TABLE 1
| Reduction of vanadium/%) | |
| Example 1 | 98.33 |
| Example 2 | 98.01 |
| Example 3 | 98.17 |
| Example 4 | 97.46 |
| Example 5 | 98.25 |
| Example 6 | 98.13 |
| Comparative example 1 | 91.68 |
| Comparative example 2 | 93.72 |
| Comparative example 3 | 95.23 |
From the test results of table 1, it can be seen that the reduction rate of vanadium is the highest when the mass ratio of the flaky vanadium pentoxide to aluminum is 1:0.5 in example 1 compared with examples 2 and 3. In contrast, in comparative examples 1 to 3, it can be seen that when the bulk vanadium pentoxide was used, the vanadium pentoxide and the reducing agent aluminum were not added simultaneously, and the argon blowing time was too long, the reduction rate of vanadium was lowered.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A method for smelting vanadium-containing alloy steel by using vanadium pentoxide to replace vanadium alloy is characterized by comprising the following steps:
adding a mixture of flaky vanadium pentoxide and aluminum into the deoxidized molten steel, blowing argon to the bottom of the steel ladle after alloying, refining and continuously casting to obtain the vanadium-containing alloy steel.
2. The method according to claim 1, wherein the mass ratio of the flaky vanadium pentoxide to the aluminum is 1: 0.4-0.6, preferably 1: 0.5.
3. The method according to any one of claims 1 to 2, wherein a refining slag and lime are added to the molten steel before the deoxidation.
4. The method according to any one of claims 1 to 3, wherein the addition amount of the refining slag is 0.2 to 0.3 percent of the mass of the molten steel;
preferably, the addition amount of the lime is 0.2-0.3% of the mass of the molten steel.
5. The method according to any one of claims 1 to 4, wherein the deoxidizing agent used in the deoxidation is aluminum.
6. The method according to claim 5, wherein the amount of the deoxidizer added is 0.1 to 0.3% by mass of the molten steel.
7. The method according to any one of claims 1 to 6, wherein the oxygen content in the deoxidized molten steel is not more than 40 ppm.
8. The method according to any one of claims 1 to 7, wherein the argon blowing time is 2 to 3 min.
9. The method according to any one of claims 1 to 8, wherein the argon blowing intensity is 0.23 to 0.45 Mpa.
10. The method according to any one of claims 1-9, characterized in that the method comprises:
adding 0.2-0.3% of refining slag and 0.2-0.3% of lime into molten steel, adding 0.1-0.3% of aluminum into the molten steel for deoxidation, adding a mixture of flaky vanadium pentoxide and aluminum into the deoxidized molten steel, wherein the mass ratio of the flaky vanadium pentoxide to the aluminum is 1: 0.4-0.6, blowing argon to the bottom of the steel ladle for 2-3 min after alloying, and the argon blowing strength is 0.23-0.45Mpa, and refining and continuous casting to obtain the vanadium-containing alloy steel.
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| JP2006299421A (en) * | 2006-06-22 | 2006-11-02 | Sumitomo Metal Ind Ltd | Method for producing v-containing steel |
| CN101067182A (en) * | 2007-06-05 | 2007-11-07 | 钢铁研究总院 | V2O5 direct alloying steelmaking technology |
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