CN113930661A - Preparation method of nitrided ferrovanadium alloy additive - Google Patents
Preparation method of nitrided ferrovanadium alloy additive Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C35/00—Master alloys for iron or steel
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
- C22C1/1057—Reactive infiltration
- C22C1/1063—Gas reaction, e.g. lanxide
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
- C22C1/1068—Making hard metals based on borides, carbides, nitrides, oxides or silicides
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/16—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on nitrides
Abstract
The invention relates to the technical field of vanadium-containing alloy production, in particular to a preparation method of a nitrided ferrovanadium alloy additive, which reduces the melting point of the nitrided ferrovanadium alloy additive, improves the density of the alloy additive and widens the application range of the nitrided ferrovanadium alloy additive by adjusting smelting raw materials and a preparation process; the nitrogen content in the alloy additive is improved by utilizing the synergistic effect between the alloy nitrogen increasing agent and the non-alloy nitrogen increasing agent; other alloy components in the smelting raw materials can supplement the element content in the molten steel, so that the consumption of the corresponding alloy raw materials is reduced, and a certain positive effect is also generated in the alloying deoxidation process of the molten steel.
Description
Technical Field
The invention relates to the technical field of production of nitrogenous alloy, and particularly relates to a preparation method of a ferrovanadium nitride alloy additive.
Background
The ferrovanadium nitride alloy is a novel alloy additive in the existing steelmaking alloying process, can replace ferrovanadium to be used for producing microalloyed steel, can increase the nitrogen content in the steel, can remove harmful impurity oxygen in molten steel, improves the comprehensive mechanical properties of the steel, such as strength, toughness, ductility, thermal fatigue resistance and the like, enables the steel to have good weldability, and can obviously reduce the cost of the alloy additive because the using amount of the ferrovanadium nitride alloy additive is 30-40 percent less than that of the ferrovanadium alloy on the premise of achieving the same strength.
With the continuous development of the steel industry, the demand of alloy additives is continuously increased, the quality requirement of the alloy additives is also continuously improved, but the problems of poor molten steel alloying efficiency and long smelting time are always existed and the steelmaking cost is also improved invisibly because the ferrovanadium nitride alloy has high melting point and low density and is difficult to meet the alloying requirements of different molten steels and enter the molten steel rapidly in the alloying process. Therefore, the development of a ferrovanadium nitride alloy additive with strong adaptability and capable of shortening the molten steel alloying time is always the key research direction of researchers.
Disclosure of Invention
The invention provides a preparation method of a ferrovanadium nitride alloy additive, aiming at the technical problems that the ferrovanadium nitride alloy additive in the prior art has low density and high melting point and is difficult to meet the requirements of various molten steel on the additive in the using process.
In order to achieve the purpose of the invention, the embodiment of the invention adopts the following technical scheme:
the embodiment of the invention provides a preparation method of a nitrided ferrovanadium alloy additive, the nitrided ferrovanadium alloy additive is prepared by smelting ferrovanadium raw materials, an alloy nitrogen increasing agent, a non-alloy nitrogen increasing agent, aluminum powder, carbon powder and ferrite serving as raw materials, and the preparation method specifically comprises the following steps:
s1: crushing a ferrovanadium alloy raw material and an alloy nitrogen increasing agent under the protection of nitrogen or inert gas, and then reserving a material with the particle size of 120-150 meshes, and crushing a non-alloy nitrogen increasing agent, aluminum powder, carbon powder and iron oxide, and then reserving a material with the particle size of 40-60 meshes;
s2: uniformly mixing a non-alloy nitrogen increasing agent, aluminum powder, carbon powder and iron oxide to obtain a component A, uniformly mixing the ferrovanadium alloy and the alloy nitrogen increasing agent to obtain a component B, adding the component A into the component B in a stirring state to obtain a well-mixed smelting raw material, and flatly paving the smelting raw material in a smelting container;
s3: and transferring the smelting container to a smelting furnace heated to a preset temperature, vacuumizing, introducing nitrogen, performing a displacement reaction in a nitrogen atmosphere, heating and continuously introducing nitrogen after the reaction is finished, igniting to perform a nitridation reaction, and cooling to room temperature in the nitrogen atmosphere after the reaction is finished to obtain the nitrided ferrovanadium alloy additive.
Compared with the prior art, the preparation method of the nitrided ferrovanadium alloy additive disclosed by the application adopts aluminum powder, carbon powder and iron oxide as smelting raw materials of the alloy, combines the replacement reaction of the carbon powder and the iron oxide with the low melting point of the aluminum powder, reduces the melting point of the nitrided ferrovanadium alloy additive, improves the density of the nitrided ferrovanadium alloy additive, and widens the application range of the nitrided ferrovanadium alloy additive; the aluminum element can also be used as a molten steel deoxidant, so that the oxygen content in molten steel is further reduced, and the molten steel smelting efficiency is improved; in the nitriding process, nitrogen can enter a product along a path left by gas generated by thermal decomposition of the non-alloy nitrogen increasing agent when the gas is discharged out of a system, meanwhile, nitrogen molecules can be fixed in the product by the excellent nitrogen fixing performance of the alloy nitrogen increasing agent, and the nitrogen molecules and the nitrogen fixing performance of the alloy nitrogen increasing agent are synergistic, so that the nitrogen content and the nitriding efficiency of the product are improved, metal elements in the alloy nitrogen increasing agent can also be used as effective components of the alloy additive, and the addition amount of corresponding alloy raw materials can also be reduced in the steelmaking process; in the smelting process, the raw materials with different particle sizes are mixed with each other and then are mixed together, the raw material with small particle size can fill the gaps among the alloy raw materials with large particle size, the mixing uniformity of the product is improved, and the synergistic effect of all the components is more easily exerted.
Preferably, the alloy nitrogen increasing agent is at least one of ferromanganese, ferrosilicon and ferrochromium, and the non-alloy nitrogen increasing agent is at least one of ammonium carbonate, ammonium bicarbonate and ammonium ferrous sulfate.
The optimized alloy nitrogen increasing agent has higher metal content and less impurities, can ensure the quality of the ferrovanadium nitride alloy additive, avoid more impurity doping, effectively control the metal element content in the alloy additive, and improve the nitrogen content; the optimized non-alloy nitrogen increasing agent can be decomposed into a plurality of gases without solid residues when being heated, the generated ammonia molecules are doped in the alloy additive, the nitrogen content of the alloy can be improved, a certain molecular path can be created when the nitrogen is discharged out of the system, the surface-to-body ratio of the alloy is improved, favorable conditions are created for the subsequent nitrogen in the nitriding reaction to enter the alloy, the nitriding reaction efficiency is improved, and the reaction time is shortened.
Preferably, the mass ratio of the ferrovanadium alloy and the alloy nitrogen increasing agent in the smelting raw materials of the ferrovanadium nitride alloy additive is 1:0.23-1.60, and the sum of the mass of the ferrovanadium alloy and the mass of the alloy nitrogen increasing agent accounts for 85% -93% of the mass of the whole raw materials.
Preferably: the pressure of nitrogen or inert gas used for protection in the S1 crushing process is more than or equal to 0.1 Mpa.
The gas protection during the crushing process can reduce the oxidation of effective components in the alloy raw materials, reduce the carrying amount of oxygen in the raw materials, avoid the oxidative deterioration of the raw materials during the smelting process and reduce the product quality.
Preferably, the thickness of the smelting raw material tiled in the smelting vessel in S2 is 100mm-500 mm.
The optimal raw material tiling thickness can ensure that the alloy raw material is heated more uniformly in the smelting process, and is also beneficial to the reduction reaction and the nitridation reaction in the smelting process, so that the alloy raw material is nitrided more completely, and the reaction rate is improved.
Preferably, the preset temperature of the smelting furnace in S3 is 600-900 ℃, the replacement reaction time is 4-6 h, and the nitrogen pressure in the smelting furnace is controlled to be more than or equal to 0.1Mpa in the replacement reaction process.
The optimized preset temperature can ensure the reduction reaction of carbon and ferric oxide while melting the aluminum powder, and simultaneously reduce the melting point of the alloy raw materials, so that the connection between the alloy raw materials is tighter, the raw materials can react more completely and fully within the oxidation reaction time of 4-6 h, and excessive oxygen inclusion is avoided.
Preferably, the temperature of the nitridation reaction in S3 is 1000-1600 ℃, the reaction time is 20-30 h, the nitrogen pressure in the nitridation reaction process is 6-15 MPa, and the nitrogen purity for maintaining the nitrogen pressure is more than or equal to 99.00%.
Under the environment of 1000-1600 ℃ and 6-15 Mpa, the alloy raw material has higher reaction activity and higher nitridation reaction rate, and the purity of nitrogen is favorable for ensuring the quality of the product, and the purer the alloy raw material is, the better the purity is in principle.
Preferably, the pressure of the nitrogen atmosphere in the smelting furnace is controlled to be more than or equal to 0.1MPa in the cooling process of S3.
Preferably, the mass percentage content of vanadium in the ferrovanadium alloy raw material is 45.00% -85.00%; the manganese content of the manganese-iron alloy in the alloy nitrogen increasing agent is 60.00-95.00% by mass, and the balance is iron and inevitable impurity elements; the silicon-iron alloy comprises 50.00-80.00% of silicon by mass and the balance of iron and inevitable impurity elements; the chromium content of the ferrochrome alloy is 52.00-72.00% by mass, and the balance is iron and inevitable impurity elements.
The application also provides a vanadium nitride ferroalloy additive prepared by the preparation method of the vanadium nitride ferroalloy additive, which specifically comprises the following elements in percentage by mass: v: 30% -40%, N: 20% -25%, nitrogen-increasing elements: 15% -25%, Al: 0.5-2%, the rest is iron and inevitable impurity elements, wherein the nitrogen-increasing element is one or more of Mn, Si or Cr elements, and the alloy is added withThe density of the additive is more than or equal to 4.5g/cm3(ii) a The melting point is less than or equal to 1200 ℃, and the method has wide application prospect.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The ferrovanadium nitride alloy additive is gradually distinguished in molten steel alloying additives due to low cost and excellent modification performance, and is more and more popular with steel mills, but different types of molten steel alloying processes with different compositions have different quality requirements on ferrovanadium nitride alloys, and the existing ferrovanadium nitride alloys can not meet the requirements of various molten steel alloying more and more no matter on melting point, nitrogen content or density, so that the alloying process is long in time, low in efficiency and poor in effect, and the cost consumption is increased invisibly.
In order to improve the modification efficiency of the nitrided ferrovanadium in the molten steel alloying process, improve the vanadium content in the nitrided ferrovanadium alloy additive and enable the application range of the nitrided ferrovanadium alloy additive to be wider, the application provides a preparation method of the nitrided ferrovanadium alloy additive, which comprises the following steps: the method adopts a ferrovanadium alloy raw material, an alloy nitrogen increasing agent, a non-alloy nitrogen increasing agent, aluminum powder, carbon powder and iron oxide as raw materials for smelting, and specifically comprises the following steps:
s1: under the protection of nitrogen or inert gas, crushing the ferrovanadium alloy and the alloy nitrogen increasing agent, and then reserving a material of 120-150 meshes, and crushing the non-alloy nitrogen increasing agent, aluminum powder, carbon powder and iron oxide, and then reserving a material of 40-60 meshes;
s2: uniformly mixing a non-alloy nitrogen increasing agent, aluminum powder, carbon powder and iron oxide to obtain a component A, uniformly mixing a vanadium-iron alloy and an alloy nitrogen increasing agent to obtain a component B, adding the component A into the component B under a stirring state to obtain a smelting raw material, and flatly paving the obtained smelting raw material in a smelting container;
s3: and transferring the smelting container to a smelting furnace heated to a preset temperature, vacuumizing, introducing nitrogen, carrying out reduction reaction in nitrogen atmosphere, heating and continuously introducing nitrogen after the reaction is finished, igniting for nitridation reaction, and continuously cooling to room temperature in nitrogen atmosphere after the reaction is finished to obtain the nitrided ferrovanadium alloy additive.
The preparation method of the nitrided ferrovanadium alloy provided by the invention realizes the technical effects of reducing the melting point, increasing the density and the nitrogen content by screening the raw materials and adjusting the preparation process: aluminum powder, carbon powder and iron oxide are used as smelting raw materials of the alloy additive, and the replacement reaction of the carbon powder and the iron oxide is combined with the low melting point of the aluminum powder, so that the melting point of the alloy additive is reduced, and the density of the alloy additive is improved; the aluminum element can also be used as a molten steel deoxidant, so that the oxygen content in molten steel is further reduced, and the molten steel smelting efficiency is improved; in the nitriding process, nitrogen can enter the alloy along a path left by gas generated by thermal decomposition of the non-alloy nitrogen increasing agent when the gas is discharged out of a system, meanwhile, nitrogen elements entering the alloy can be fixed in the product by the excellent nitrogen fixation performance of the alloy nitrogen increasing agent, and the nitrogen elements and the nitrogen fixation performance of the alloy nitrogen increasing agent are synergistic with each other, so that the nitrogen content and the nitriding efficiency of the product are improved together, metal elements in the alloy nitrogen increasing agent also belong to effective components serving as alloy additives, and the addition amount of corresponding alloy raw materials can be reduced in the steelmaking process; in the smelting process, the raw materials with different particle sizes are mixed with each other and then are mixed together, the raw material with small particle size can fill the gaps among the alloy raw materials with large particle size, the mixing uniformity of the product is improved, and the synergistic effect of all the components is exerted more easily.
In order to ensure the basic properties and the metal content of the ferrovanadium nitride alloy additive, the mass ratio of the ferrovanadium alloy for preparing the ferrovanadium nitride alloy additive to the alloy nitrogen increasing agent is 1:0.23-1.60, and the mass sum of the ferrovanadium alloy and the alloy nitrogen increasing agent accounts for 85% -93% of the total smelting raw materials.
The nitrogen increasing agent should avoid excessive impurity doping as much as possible, and should be selected according to the principle of less impurity and no residue. Illustratively, the alloy nitrogen increasing agent adopted by the application is at least one of ferromanganese, ferrosilicon and ferrochrome, and the non-alloy nitrogen increasing agent adopted is at least one of ammonium carbonate, ammonium bicarbonate and ammonium ferrous sulfate.
During smelting, the stability of the components of the alloy raw materials is protected, excessive oxygen carried in the alloy raw materials is avoided, the alloy raw materials are prevented from being oxidized and deteriorated in the smelting process, the crushing process of the raw materials is carried out in the protective atmosphere of nitrogen or inert gas, and the pressure of the nitrogen or inert gas for protection is more than or equal to 0.1 Mpa.
In the smelting process, in order to ensure that the smelting raw materials are heated in the smelting container more uniformly and ensure that the replacement reaction and the nitridation reaction have higher efficiency, the thickness of the smelting raw materials spread in the smelting container in S2 is between 100mm and 500 mm.
The preset temperature of the smelting furnace is to ensure that aluminum powder is molten and the carbon and the iron oxide are subjected to a displacement reaction, the melting point of alloy raw materials is reduced by utilizing the synergistic effect of the aluminum powder and the iron oxide, the intermolecular connection is tighter, and the optimal temperature is 600-900 ℃; the time length of the oxidation reaction is selected to ensure that the oxidation reaction is complete and excessive energy consumption is avoided, and the optimal time is 4-6 h; similarly, in S3, the nitriding reaction temperature is 1000-1600 ℃, the nitriding reaction time is 20-30 h, the nitrogen pressure in the nitriding reaction process is 6-15 Mpa, the nitrogen purity for maintaining the nitrogen pressure is more than or equal to 99.00%, and the pressure of the nitrogen atmosphere in the smelting furnace is more than or equal to 0.1Mpa in the cooling process after the nitriding reaction.
By way of illustration, the vanadium content of the vanadium iron alloy raw material used in the present application should be rich and not contain excessive impurities, and the mass percentage of vanadium is preferably 45.00-85.00%. The same is true for the selection criteria of the alloy nitrogen increasing agent, and for example, when the ferromanganese is selected as the alloy nitrogen increasing agent, the manganese content in the ferromanganese is 60.00-95.00% by mass, and the balance of iron and inevitable impurity elements; when the ferrosilicon is selected as the alloy nitrogen increasing agent, the mass percentage of silicon in the ferrosilicon is 50.00-80.00%, and the balance is iron and inevitable impurity elements; when the ferrochrome is selected as the alloy nitrogen increasing agent, the mass percentage of chromium in the ferrochrome is 52.00-72.00%, and the balance is iron and inevitable impurity elements.
The invention is further illustrated below in the following examples.
Example 1
The embodiment provides a preparation method of a nitrided ferrovanadium alloy additive, which comprises the following raw materials: 10kg of ferrovanadium, 6.28kg of ferromanganese, 0.5kg of ammonium bicarbonate, 0.25kg of aluminum powder, 0.2kg of carbon powder and 0.4kg of ferric oxide, wherein the ratio of TV: 79.82%, and the ratio of TMn in the manganese-iron alloy raw materials: 78.23%, and the balance of Fe and small amount of impurity elements.
The preparation method of the nitrided ferrovanadium alloy additive specifically comprises the following steps:
s1: crushing a ferrovanadium alloy and a ferromanganese alloy under the protection of nitrogen, and then reserving a material of 120-150 meshes, and crushing ammonium bicarbonate, aluminum powder, carbon powder and ferric oxide, and then reserving a material of 40-60 meshes;
s2: uniformly mixing ammonium bicarbonate, aluminum powder, carbon powder and ferric oxide to obtain a component A, uniformly mixing ferrovanadium alloy and ferromanganese alloy to obtain a component B, adding the component A into the component B in a stirring state, uniformly mixing to obtain a well-mixed smelting raw material, and flatly paving the smelting raw material in a graphite crucible to form a raw material layer with the thickness of 200 mm;
s3: transferring the graphite crucible to a vacuum smelting furnace preheated to 700 ℃, immediately vacuumizing and introducing nitrogen, performing replacement reaction for 5 hours in an environment with the nitrogen atmosphere being more than or equal to 0.1Mpa, heating to 1300 ℃ after the reaction is finished, introducing nitrogen with the purity being more than or equal to 99%, igniting under the nitrogen pressure of 10Mpa for nitriding combustion, stopping heating after the reaction is performed for 25 hours, maintaining the nitrogen atmosphere in the furnace to be more than or equal to 0.1Mpa, and cooling for 9 hours to obtain the nitrided ferrovanadium alloy additive.
Through detection, the mass content of each element in the obtained ferrovanadium nitride alloy additive is V: 37.70%, Mn: 23.32%, N: 20.43%, Al: 1.19 percent of iron and inevitable impurity elements, and the obtained ferrovanadium alloy additive has the apparent density of 4.57g/cm3The melting point is 1100 ℃.
Example 2
The embodiment provides a preparation method of a nitrided ferrovanadium alloy additive, which comprises the following raw materials: 10kg ferrovanadium, 6.5kg ferrosilicon, 0.4kg ammonium ferrous sulfate, 0.3kg aluminum powder, 0.3kg carbon powder and 0.5kg ferroferric oxide, wherein the raw materials of the ferrovanadium include TV: 79.47%, TSi in the raw materials of the ferrosilicon alloy: 75.16 percent, and the balance of iron and a small amount of impurity elements.
The preparation method of the nitrided ferrovanadium alloy additive specifically comprises the following steps:
s1: under the protection of argon, crushing ferrovanadium and ferrosilicon, and then reserving a material of 120-150 meshes, and crushing ammonium ferrous sulfate, aluminum powder, carbon powder and ferroferric oxide, and then reserving a material of 40-60 meshes;
s2: uniformly mixing ammonium ferrous sulfate, aluminum powder, carbon powder and ferroferric oxide to obtain a component A, uniformly mixing a vanadium iron alloy and a silicon iron alloy to obtain a component B, adding the component A into the component B in a stirring state, uniformly mixing to obtain a well-mixed smelting raw material, and flatly paving the smelting raw material in a graphite crucible to form a raw material layer with the thickness of 300 mm;
s3: transferring the graphite crucible to a vacuum smelting furnace preheated to 800 ℃, immediately vacuumizing and introducing nitrogen, performing replacement reaction for 4.5 hours in an environment with the nitrogen atmosphere being more than or equal to 0.1Mpa, heating to 1200 ℃ after the reaction is finished, introducing nitrogen with the purity being more than or equal to 99%, igniting under the nitrogen pressure of 12Mpa for nitriding combustion, stopping heating after the reaction is performed for 24 hours, maintaining the nitrogen atmosphere in the furnace to be more than or equal to 0.1Mpa, and cooling for 8 hours to obtain the nitrided ferrovanadium alloy additive.
Through detection, the mass content of each element in the obtained ferrovanadium nitride alloy additive is V: 36.58%, Si: 22.80%, N: 20.47%, Al: 1.40 percent of the vanadium iron alloy additive, and the balance of iron and inevitable impurity elements, wherein the apparent density of the obtained vanadium iron alloy additive is 4.51g/cm3The melting point is 1035 ℃.
Example 3
The embodiment provides a preparation method of a nitrided ferrovanadium alloy additive, which comprises the following raw materials: 10kg of ferrovanadium, 4.7kg of ferrochromium, 0.25kg of ammonium ferrous sulfate, 0.25kg of aluminum powder, 0.2kg of carbon powder and 0.4kg of ferroferric oxide, wherein the ratio of TV: 70.49%, and the content of TCr in the ferrochrome raw material is as follows: 65.73%, and the balance of Fe and small amount of impurity elements.
The preparation method of the nitrided ferrovanadium alloy additive specifically comprises the following steps:
s1: under the protection of nitrogen, crushing ferrovanadium and ferrochromium, and then reserving a material of 120 meshes and 150 meshes, and crushing ammonium ferrous sulfate, aluminum powder, carbon powder and ferroferric oxide, and then reserving a material of 40-60 meshes;
s2: uniformly mixing ammonium ferrous sulfate, aluminum powder, carbon powder and ferroferric oxide to obtain a component A, uniformly mixing ferrovanadium and ferrochromium to obtain a component B, adding the component A into the component B in a stirring state, uniformly mixing to obtain a well-mixed smelting raw material, and flatly paving the smelting raw material in a graphite crucible to form a raw material layer with the thickness of 280 mm;
s3: transferring the graphite crucible to a vacuum smelting furnace preheated to 900 ℃, immediately vacuumizing and introducing nitrogen, carrying out reduction reaction for 5 hours in an environment with the nitrogen atmosphere being more than or equal to 0.1Mpa, heating to 1300 ℃ after the reaction is finished, introducing nitrogen with the purity being more than or equal to 99%, igniting under the nitrogen pressure of 14Mpa for nitriding combustion, stopping heating after the reaction is carried out for 30 hours, maintaining the nitrogen atmosphere in the furnace to be more than or equal to 0.1Mpa, and cooling for 9 hours to obtain the nitrided ferrovanadium alloy additive.
Through detection, the mass content of each element in the obtained ferrovanadium nitride alloy additive is V: 37.05%, Cr: 16.24%, N: 21.03%, Al: 1.3 percent of iron and inevitable impurity elements, and the obtained ferrovanadium alloy additive has the apparent density of 4.62g/cm3The melting point was 1075 ℃.
Example 4
The embodiment provides a preparation method of a nitrided ferrovanadium alloy additive, which comprises the following raw materials: 10kg ferrovanadium, 2.8kg ferrochromium, 2.0kg ferrosilicon, 0.2kg ammonium bicarbonate, 0.1kg ammonium bicarbonate, 0.3kg aluminium powder, 0.2kg carbon powder and 0.4kg ferric oxide, wherein in the ferrovanadium raw material TV: 69.48%, and the content of TCr in the ferrochrome raw material is as follows: 65.73%, TSi in the raw materials of the ferrosilicon alloy: 75.16 percent, and the balance of iron and a small amount of impurity elements.
The preparation method of the nitrided ferrovanadium alloy additive specifically comprises the following steps:
s1: under the protection of nitrogen, crushing ferrovanadium, ferrochromium and ferrosilicon, and then reserving materials of 120-150 meshes, and crushing ammonium bicarbonate, ammonium carbonate, aluminum powder, carbon powder and ferric oxide, and then reserving materials of 40-60 meshes;
s2: uniformly mixing ammonium bicarbonate, ammonium carbonate, aluminum powder, carbon powder and ferric oxide to obtain a component A, uniformly mixing ferrovanadium, ferrochromium and ferrosilicon to obtain a component B, adding the component A into the component B in a stirring state, uniformly mixing to obtain a well-mixed smelting raw material, and flatly paving the smelting raw material in a graphite crucible to form a raw material layer with the thickness of 340 mm;
s3: transferring the graphite crucible to a vacuum smelting furnace preheated to 800 ℃, immediately vacuumizing and introducing nitrogen, carrying out reduction reaction for 4.5h in an environment with the nitrogen atmosphere being more than or equal to 0.1Mpa, heating to 1200 ℃ after the reaction is finished, introducing nitrogen with the purity being more than or equal to 99%, igniting under the nitrogen pressure of 12Mpa for nitriding combustion, stopping heating after the reaction is carried out for 26h, maintaining the nitrogen atmosphere in the furnace to be more than or equal to 0.1Mpa, and cooling for 7h to obtain the nitrided ferrovanadium alloy additive.
Through detection, the mass content of each element in the obtained ferrovanadium nitride alloy additive is V: 35.17%, Cr: 9.32%, Si: 6.74%, N: 21.06%, Al: 1.46 percent of iron and inevitable impurity elements, and the obtained ferrovanadium alloy additive has the apparent density of 4.58g/cm3The melting point is 1035 ℃.
Example 5
The embodiment provides a preparation method of a nitrided ferrovanadium alloy additive, which comprises the following raw materials: 10kg ferrovanadium, 2.8kg ferrochromium, 2.0kg ferrosilicon, 1.9kg ferromanganese, 0.4kg ammonium bicarbonate, 0.2kg ammonium ferrous sulfate, 0.4kg aluminum powder, 0.3kg carbon powder and 0.5kg ferric oxide, wherein the ratio of TV: 82.23%, and the content of TCr in the ferrochrome raw material is as follows: 65.96%, TSi in the raw materials of the ferrosilicon alloy: 78.23%, and the ratio of TMn in the manganese-iron alloy raw materials: 75.16 percent, and the balance of iron and a small amount of impurity elements.
The preparation method of the nitrided ferrovanadium alloy additive specifically comprises the following steps:
s1: under the protection of nitrogen, crushing ferrovanadium, ferromanganese, ferrochromium and ferrosilicon, then reserving a material with the particle size of 120-150 meshes, and crushing ammonium bicarbonate, ammonium ferrous sulfate, aluminum powder, carbon powder and ferric oxide, and then reserving a material with the particle size of 40-60 meshes;
s2: uniformly mixing ammonium bicarbonate, ammonium ferrous sulfate, aluminum powder, carbon powder and ferric oxide to obtain a component A, uniformly mixing ferrovanadium, ferromanganese, ferrochromium and ferrosilicon to obtain a component B, adding the component A into the component B in a stirring state, uniformly mixing to obtain a well-mixed smelting raw material, and flatly paving the smelting raw material in a graphite crucible to form a raw material layer with the thickness of 400 mm;
s3: transferring the graphite crucible to a vacuum smelting furnace preheated to 850 ℃, immediately vacuumizing and introducing nitrogen, carrying out reduction reaction for 5.5h in an environment with the nitrogen atmosphere being more than or equal to 0.1Mpa, heating to 1400 ℃ after the reaction is finished, introducing nitrogen with the purity being more than or equal to 99%, igniting under the nitrogen pressure of 14Mpa for nitriding combustion, stopping heating after 28h of reaction, maintaining the nitrogen atmosphere in the furnace to be more than or equal to 0.1Mpa, and cooling for 9h to obtain the nitrided ferrovanadium alloy additive.
Through detection, the mass content of each element in the obtained ferrovanadium nitride alloy additive is V: 37.48%, Cr: 8.1%, Mn: 6.83%, Si: 5.01%, N: 20.58%, Al: 1.8 percent of iron and inevitable impurity elements, and the apparent density of the obtained ferrovanadium alloy additive is 4.55g/cm3The melting point is 1050 ℃.
Comparative example 1
The comparative example provides a preparation method of a nitrided ferrovanadium alloy additive, and the used raw materials comprise: 10kg of ferrovanadium, 6.28kg of ferromanganese, 0.25kg of aluminum powder, 0.2kg of carbon powder and 0.4kg of ferric oxide, wherein the raw materials of the ferrovanadium alloy comprise TV: 79.82%, and the ratio of TMn in the manganese-iron alloy raw materials: 78.23%, and the balance of Fe and small amount of impurity elements.
The preparation method of the nitrided ferrovanadium alloy additive specifically comprises the following steps:
s1: under the condition of nitrogen protection, crushing a ferrovanadium alloy raw material and a ferromanganese alloy, and then reserving a material of 120-150 meshes, and crushing aluminum powder, carbon powder and ferric oxide, and then reserving a material of 40-60 meshes;
s2: uniformly mixing aluminum powder, carbon powder and ferric oxide to obtain a component A, uniformly mixing ferrovanadium alloy and ferromanganese alloy to obtain a component B, adding the component A into the component B in a stirring state, uniformly mixing to obtain a well-mixed smelting raw material, and flatly paving the smelting raw material in a graphite crucible to form a raw material layer with the thickness of 200 mm;
s3: transferring the graphite crucible to a vacuum smelting furnace preheated to 700 ℃, immediately vacuumizing and introducing nitrogen, carrying out reduction reaction for 5 hours in an environment with the nitrogen atmosphere being more than or equal to 0.1Mpa, heating to 1300 ℃ after the reaction is finished, introducing nitrogen with the purity being more than or equal to 99%, igniting under the nitrogen pressure of 10Mpa for nitriding combustion, stopping heating after the reaction is carried out for 25 hours, maintaining the nitrogen atmosphere in the furnace to be more than or equal to 0.1Mpa, and cooling for 9 hours to obtain the nitrided ferrovanadium alloy additive.
Through detection, the mass content of each element in the obtained ferrovanadium nitride alloy additive is V: 38.06%, Mn: 23.83%, N: 15.43%, Al: 1.04 percent of iron and inevitable impurity elements, and the obtained ferrovanadium alloy additive has the apparent density of 4.36g/cm3The melting point is 1150 ℃.
Comparative example 2
The comparative example provides a preparation method of a nitrided ferrovanadium alloy additive, and the used raw materials comprise: 10kg of ferrovanadium, 6.28kg of ferromanganese, 0.5kg of ammonium bicarbonate, 0.2kg of carbon powder and 0.4kg of ferric oxide, wherein the ratio of TV: 79.82%, and the ratio of TMn in the manganese-iron alloy raw materials: 78.23%, and the balance of Fe and small amount of impurity elements.
The preparation method of the nitrided ferrovanadium alloy additive specifically comprises the following steps:
s1: under the condition of nitrogen protection, crushing a ferrovanadium raw material and a ferromanganese alloy, and then reserving a material of 120-150 meshes, and crushing ammonium bicarbonate, carbon powder and ferric oxide, and then reserving a material of 40-60 meshes;
s2: uniformly mixing ammonium bicarbonate, carbon powder and ferric oxide to obtain a component A, uniformly mixing ferrovanadium alloy and ferromanganese alloy to obtain a component B, adding the component A into the component B in a stirring state, uniformly mixing to obtain a well-mixed smelting raw material, and flatly paving the smelting raw material in a graphite crucible to form a raw material layer with the thickness of 200 mm;
s3: transferring the graphite crucible to a vacuum smelting furnace preheated to 700 ℃, immediately vacuumizing and introducing nitrogen, carrying out reduction reaction for 5 hours in an environment with the nitrogen atmosphere being more than or equal to 0.1Mpa, heating to 1300 ℃ after the reaction is finished, introducing nitrogen with the purity being more than or equal to 99%, igniting under the nitrogen pressure of 10Mpa for nitriding combustion, stopping heating after the reaction is carried out for 25 hours, maintaining the nitrogen atmosphere in the furnace to be more than or equal to 0.1Mpa, and cooling for 9 hours to obtain the nitrided ferrovanadium alloy additive.
Through detection, the mass content of each element in the obtained ferrovanadium nitride alloy additive is V: 37.54%, Mn: 23.42%, N: 19.86 percent of iron and inevitable impurity elements, and the obtained ferrovanadium alloy additive has the apparent density of 3.98g/cm3The melting point was 1300 ℃.
Comparative example 3
The embodiment provides a preparation method of a nitrided ferrovanadium alloy additive, which comprises the following raw materials: 10kg of ferrovanadium alloy, 6.28kg of ferromanganese alloy, 0.5kg of ammonium bicarbonate and 0.25kg of aluminum powder, wherein the ratio of TV: 79.82%, and the ratio of TMn in the manganese-iron alloy raw materials: 78.23%, and the balance of Fe and small amount of impurity elements.
The preparation method of the nitrided ferrovanadium alloy additive specifically comprises the following steps:
s1: crushing the ferrovanadium alloy and the ferromanganese alloy under the protection of nitrogen, and then reserving a material of 120-150 meshes, and crushing the ammonium bicarbonate and the aluminum powder, and then reserving a material of 40-60 meshes;
s2: uniformly mixing ammonium bicarbonate and aluminum powder to obtain a component A, uniformly mixing a ferrovanadium alloy and a ferromanganese alloy to obtain a component B, adding the component A into the component B in a stirring state, uniformly mixing to obtain a well-mixed smelting raw material, and flatly paving the smelting raw material in a graphite crucible to form a raw material layer with the thickness of 200 mm;
s3: transferring the graphite crucible to a vacuum smelting furnace preheated to 700 ℃, immediately vacuumizing and introducing nitrogen, performing replacement reaction for 5 hours in an environment with the nitrogen atmosphere being more than or equal to 0.1Mpa, heating to 1300 ℃ after the reaction is finished, introducing nitrogen with the purity being more than or equal to 99%, igniting under the nitrogen pressure of 10Mpa for nitriding combustion, stopping heating after the reaction is performed for 25 hours, maintaining the nitrogen atmosphere in the furnace to be more than or equal to 0.1Mpa, and cooling for 9 hours to obtain the nitrided ferrovanadium alloy additive.
Through detection, the mass content of each element in the obtained ferrovanadium nitride alloy additive is V: 37.48%, Mn: 23.66%, N: 19.35%, Al: 1.02 percent of iron and inevitable impurity elements, and the apparent density of the obtained ferrovanadium alloy additive is 4.02g/cm3The melting point was 1350 ℃.
The above description is only exemplary of the present invention and should not be taken as limiting, and any modifications, equivalents, improvements, etc. that are made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The preparation method of the nitrided ferrovanadium alloy additive is characterized in that the nitrided ferrovanadium alloy additive is prepared by smelting ferrovanadium alloy, an alloy nitrogen increasing agent, a non-alloy nitrogen increasing agent, aluminum powder, carbon powder and iron oxide serving as raw materials, and specifically comprises the following steps:
s1: crushing the ferrovanadium alloy and the alloy nitrogen increasing agent to 120-150 meshes under the protection of nitrogen or inert gas, and crushing the non-alloy nitrogen increasing agent, aluminum powder, carbon powder and iron oxide to 40-60 meshes;
s2: uniformly mixing the non-alloy nitrogen increasing agent, aluminum powder, carbon powder and iron oxide to obtain a component A, uniformly mixing the ferrovanadium alloy and the alloy nitrogen increasing agent to obtain a component B, adding the component A into the component B under the stirring state to obtain a smelting raw material, and flatly paving the smelting raw material in a smelting container;
s3: and transferring the smelting container to a smelting furnace heated to a preset temperature, vacuumizing, introducing nitrogen, performing a displacement reaction in a nitrogen atmosphere, heating and continuously introducing nitrogen after the reaction is finished, igniting to perform a nitridation reaction, and cooling to room temperature in the nitrogen atmosphere after the reaction is finished to obtain the nitrided ferrovanadium alloy additive.
2. The method of claim 1, wherein the alloy nitrogen increasing agent is at least one of ferromanganese, ferrosilicon and ferrochrome, and the non-alloy nitrogen increasing agent is at least one of ammonium carbonate, ammonium bicarbonate and ammonium ferrous sulfate.
3. The method for preparing the nitrided ferrovanadium alloy additive as claimed in claim 2, wherein the mass ratio of ferrovanadium to the alloy nitrogen increasing agent in the smelting raw materials of the ferrovanadium alloy additive is 1:0.23-1.60, and the sum of the mass of the ferrovanadium and the mass of the alloy nitrogen increasing agent accounts for 85% -93% of the mass of the whole raw materials.
4. The method for preparing a nitrided ferrovanadium alloy additive as claimed in claim 1, wherein the pressure of nitrogen or inert gas used for protection in the crushing process of S1 is not less than 0.1 Mpa.
5. The method for preparing the nitrided ferrovanadium alloy additive according to claim 1, wherein the thickness of the flat spread of the smelting raw material in the smelting vessel in S2 is 100mm to 500 mm.
6. The method for preparing the nitrided ferrovanadium alloy additive according to claim 1, wherein the preset temperature in S3 is 600 ℃ to 900 ℃, the replacement reaction time is 4h to 6h, and the nitrogen pressure in the smelting furnace is controlled to be more than or equal to 0.1MPa in the replacement reaction process.
7. The method for preparing the nitrided ferrovanadium alloy additive as claimed in claim 1, wherein the nitriding reaction temperature in S3 is 1000 ℃ to 1600 ℃, the reaction time is 20h to 30h, the nitrogen pressure in the nitriding reaction process is 6Mpa to 15Mpa, and the nitrogen purity for maintaining the nitrogen pressure is not less than 99.00%.
8. The method for preparing the nitrided ferrovanadium alloy additive according to claim 1, wherein the pressure of the nitrogen atmosphere in the smelting furnace is controlled to be not less than 0.1Mpa during the cooling process in S3.
9. The method for preparing the nitrided ferrovanadium alloy additive of claim 2, wherein the mass percentage content of vanadium in the ferrovanadium alloy raw material is 45.00-85.00%; and/or
The manganese-iron alloy in the alloy nitrogen increasing agent comprises 60.00-95.00% of manganese by mass, and the balance of iron and inevitable impurity elements; and/or
The ferrosilicon alloy comprises 50.00-80.00% of silicon by mass and the balance of iron and inevitable impurity elements; and/or
The chromium-iron alloy comprises, by mass, 52.00-72.00% of chromium and the balance of iron and inevitable impurity elements.
10. The ferrovanadium nitride alloy additive is prepared by the preparation method of the ferrovanadium nitride alloy additive disclosed by any one of claims 1-9, and specifically comprises the following elements in percentage by mass: v: 30% -40%, N: 20% -25%, nitrogen-increasing elements: 15% -20%, Al: 0.5 to 2 percent of iron and the balance of inevitable impurity elements, wherein the nitrogen increasing element is one or more of Mn, Si or Cr elements.
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| CN111607730A (en) * | 2020-06-28 | 2020-09-01 | 承德锦科科技股份有限公司 | Vanadium nitride niobium iron alloy and preparation method and application thereof |
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| GB1307817A (en) * | 1969-03-27 | 1973-02-21 | Murex Ltd | Nitrogen-containing alloys |
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