Preparation method of low-vanadium ferromanganese alloy material

Abstract

The invention belongs to the technical field of alloy materials, and relates to a preparation method of a low-vanadium ferromanganese alloy material. The preparation method provided by the invention comprises the following steps: crushing the calcium-containing vanadium slag, and screening to obtain the calcium-containing vanadium slag with the particle size of 5-120mm and the calcium-containing vanadium slag with the particle size of less than 5mm; the vanadium-containing tailings are screened, and the vanadium-containing tailings with the particle size being smaller than 5 mm are obtained; the calcium-containing vanadium slag with the particle size smaller than 5 mm, the vanadium-containing tailings with the particle size smaller than 5 mm and a binder are mixed and pressed into balls, and spherical particles are obtained; the method comprises the following steps: detecting chemical components in the calcium-containing vanadium slag, the vanadium-containing tailings, the ferrovanadium ore and the manganese ore, calculating the material dosage according to the detection result, and mixing the calcium-containing vanadium slag with the particle size of 5-120mm, the spherical particles, the ferrovanadium ore, the manganese ore, an iron source, a reducing agent and a pH regulator according to the calculation result for smelting to obtain the low-vanadium ferromanganese alloy material. The smelting waste slag is used as a preparation raw material, so that the production cost of the vanadium-containing alloy is reduced while the waste slag is effectively treated.

Description

Technical Field

[0001] The invention belongs to the technical field of alloy materials, and in particular relates to a method for preparing a low-vanadium manganese iron alloy material. Background Art

[0002] As the frequency of earthquakes increases, the requirements for earthquake resistance of buildings are gradually increasing. At present, the direct way to improve the earthquake resistance of buildings is to improve the earthquake resistance of steel bars. As an important alloying element in alloy steel, adding 3‰ of vanadium can increase the strength, toughness, ductility and fatigue of the original steel bars by 20-30%. It is mainly used for high-strength steels such as earthquake-resistant threaded steel, ship plate steel, automobile, and train steel beams. However, the high price of vanadium has increased the price of vanadium-manganese special steels, limiting the promotion and application of vanadium-containing alloy steels. Summary of the invention

[0003] In view of this, the present invention provides a method for preparing a low-vanadium ferromanganese alloy material. The present invention uses waste materials such as calcium-vanadium slag and vanadium-containing tailings as raw materials to prepare the low-vanadium ferromanganese alloy material, which greatly reduces the production cost of the vanadium-containing alloy and expands its application range.

[0004] In order to solve the above technical problems, the present invention provides a method for preparing a low-vanadium manganese iron alloy material, comprising the following steps:

[0005] The calcium-vanadium-containing slag is crushed and then sieved to obtain calcium-vanadium-containing slag with a particle size of 5 to 120 mm and calcium-vanadium-containing slag with a particle size of less than 5 mm;

[0006] Screening the vanadium-containing tailings to obtain vanadium-containing tailings with a particle size of less than 5 mm;

[0007] The calcium-vanadium-containing slag with a particle size of less than 5 mm, the vanadium-containing tailings with a particle size of less than 5 mm and a binder are mixed and pressed into balls to obtain spherical particles;

[0008] The chemical components of calcium-vanadium-containing slag, vanadium-containing tailings, vanadium iron ore and manganese ore are detected, and the material dosage is calculated according to the detection results. According to the calculated results, the calcium-vanadium-containing slag with a particle size of 5 to 120 mm, spherical particles, vanadium iron ore, manganese ore, iron source, reducing agent and pH regulator are mixed and smelted to obtain low-vanadium manganese iron alloy material.

[0009] Preferably, the iron source includes steel scraps, iron oxide scale or iron ore with an iron content greater than 55%;

[0010] The pH regulator is one or more of silica, silicon slag and dolomite.

[0011] Preferably, the mass percentage of manganese in the manganese ore is greater than 45%, and the mass percentage of phosphorus is less than 0.08%.

[0012] Preferably, the reducing agent is blue charcoal and / or coke;

[0013] The thermal strength of the coke is >55.

[0014] Preferably, when the reducing agent is blue charcoal and coke, the mass ratio of the coke to blue charcoal is 1:1 to 1:3.

[0015] Preferably, the smelting is carried out in a submerged arc furnace, the smelting temperature is 1600-1700° C., and the smelting time is 180-220 min.

[0016] Preferably, the diameter of the spherical particles is greater than 38 mm.

[0017] Preferably, the mixing of calcium-vanadium-containing slag, spherical particles, vanadium iron ore, manganese ore, iron source, reducing agent and pH regulator comprises the following steps:

[0018] The calcium-vanadium-containing slag, the spherical particles, the vanadium iron ore and the manganese ore are first mixed to obtain a first mixture;

[0019] The pH regulator and the first mixture are mixed for a second time to adjust the pH to 0.8±0.2 to obtain a second mixture;

[0020] The reducing agent, the iron source and the second mixture are subjected to a third mixing.

[0021] Preferably, the amount of each material used in the process of mixing the calcium-vanadium-containing slag, spherical particles, vanadium iron ore, manganese ore, iron source, reducing agent and pH regulator is determined by a computer through an automatic batching system.

[0022] Preferably, the mixing before smelting also includes: crushing and screening the vanadium iron ore and manganese ore.

[0023] The present invention provides a method for preparing a low-vanadium manganese ferroalloy material, comprising the following steps: crushing and screening calcium-vanadium-containing slag to obtain calcium-vanadium-containing slag with a particle size of 5 to 120 mm and calcium-vanadium-containing slag with a particle size of less than 5 mm; screening vanadium-containing tailings to obtain vanadium-containing tailings with a particle size of less than 5 mm; mixing and pressing calcium-vanadium-containing slag with a particle size of less than 5 mm, vanadium-containing tailings with a particle size of less than 5 mm and a binder to obtain spherical particles; detecting the chemical components in calcium-vanadium-containing slag, vanadium-containing tailings, vanadium iron ore and manganese ore, calculating the material dosage according to the detection results, and mixing calcium-vanadium-containing slag with a particle size of 5 to 120 mm, spherical particles, vanadium iron ore, manganese ore, iron source, reducing agent and pH regulator according to the calculation results for smelting to obtain low-vanadium manganese ferroalloy material. The present invention mainly uses smelting waste slag as the preparation raw material, and reduces the production cost of vanadium-containing alloy while effectively treating the waste slag. The low-vanadium manganese iron alloy material provided by the present invention can replace (all or part of) the use of electrolytic manganese, high-vanadium iron or vanadium-nitrogen alloy, thereby reducing the production cost of vanadium-manganese alloy steel produced by steel plants. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 Schematic diagram of the process for preparing low-vanadium manganese iron alloy materials. DETAILED DESCRIPTION

[0025] The present invention provides a method for preparing a low-vanadium manganese iron alloy material, comprising the following steps:

[0026] The calcium-vanadium-containing slag is crushed and then sieved to obtain calcium-vanadium-containing slag with a particle size of 5 to 120 mm and calcium-vanadium-containing slag with a particle size of less than 5 mm;

[0027] Screening the vanadium-containing tailings to obtain vanadium-containing tailings with a particle size of less than 5 mm;

[0028] The calcium-vanadium-containing slag with a particle size of less than 5 mm, the vanadium-containing tailings with a particle size of less than 5 mm and a binder are mixed and pressed into balls to obtain spherical particles;

[0029] The chemical components of calcium-vanadium-containing slag, spherical particles, vanadium iron ore and manganese ore are detected, the material dosage is calculated according to the detection results, and the calcium-vanadium-containing slag, spherical particles, vanadium iron ore, manganese ore, iron source, reducing agent and pH regulator with a particle size of 5 to 120 mm are mixed and smelted according to the calculated results to obtain low-vanadium manganese iron alloy material.

[0030] The present invention crushes the calcium-vanadium-containing slag and then screens it to obtain calcium-vanadium-containing slag with a particle size of 5 to 120 mm and calcium-vanadium-containing slag with a particle size of less than 5 mm. In the present invention, the vanadium-containing tailings are preferably tailings produced in the process of making vanadium (V2O5). The present invention has no special requirements for the crushing, and the conventional method in the art can be used. The present invention preferably further screens the calcium-vanadium-containing slag with a particle size of 5 to 120 mm to obtain multi-graded calcium-vanadium-containing slag; the particle size of the multi-graded calcium-vanadium-containing slag is preferably greater than or equal to 5 mm and less than 30 mm, greater than or equal to 30 mm and less than 50 mm, greater than or equal to 50 mm and less than 80 mm, and greater than or equal to 80 mm and less than 120 mm. The present invention can improve the recovery rate of vanadium, iron, manganese and silicon in the calcium-vanadium-containing slag by adding calcium-vanadium-containing slag of different particle sizes during the smelting process, and can make the recovery rate of vanadium, iron, manganese and silicon in the calcium-vanadium-containing slag greater than 90%.

[0031] The present invention screens the vanadium-containing tailings to obtain vanadium-containing tailings with a particle size of less than 5 mm. The present invention has no special requirements for the screening, and a conventional method in the art can be used.

[0032] After obtaining calcium-vanadium-containing slag with a particle size of less than 5mm and vanadium-containing tailings with a particle size of less than 5mm, the present invention mixes the calcium-vanadium-containing slag with a particle size of less than 5mm, the vanadium-containing tailings with a particle size of less than 5mm and a binder for ball pressing to obtain spherical particles. In the present invention, the binder is preferably a resin binder; the resin binder is preferably a fully soluble resin binder. In the present invention, the binder is used to bond the calcium-vanadium-containing slag with a particle size of less than 5mm and the vanadium-containing tailings with a particle size of less than 5mm into shape. The present invention has no special requirements for the model and amount of the binder, as long as it can be formed. In the present invention, the diameter of the spherical particles is preferably greater than 38mm, more preferably 48-52mm, and further preferably 50mm. The present invention has no special requirements for the mixing and ball pressing methods, and the conventional methods in the art can be used. The purpose of ball pressing in the present invention is to avoid directly adding powder raw materials into the blast furnace to affect the air permeability.

[0033] The present invention detects the chemical components in calcium-vanadium slag, spherical particles, vanadium iron ore and manganese ore, calculates the material dosage according to the detection results, and mixes the calcium-vanadium slag, spherical particles, vanadium iron ore, manganese ore, iron source, reducing agent and pH regulator with a particle size of 5 to 120 mm for smelting according to the calculation results to obtain a low-vanadium manganese iron alloy material. In the present invention, the mass percentage of manganese in the manganese ore is preferably 45% or more, more preferably 48 to 55%; the mass percentage of phosphorus in the manganese ore is preferably 0.08% or less, more preferably 0.01 to 0.05%. In the present invention, the iron source preferably includes steel scraps, iron oxide scale or iron ore with an iron content greater than 55%, more preferably steel scraps. In the present invention, the iron content of the steel scraps is preferably 99% or more. In the present invention, the reducing agent is blue charcoal and / or coke, preferably blue charcoal and coke; the thermal strength of the coke is preferably>55. In the present invention, when the reducing agent is coke and blue charcoal, the mass ratio of the coke to blue charcoal is 1:1 to 1:3. In the present invention, the coke can also increase the permeability during the smelting process. In the present invention, the pH regulator is one or more of silica, silicon slag and dolomite, more preferably silica or silicon slag, and more preferably silica.

[0034] The present invention preferably detects the contents of vanadium, iron, manganese, phosphorus, silicon dioxide, magnesium oxide, calcium oxide and aluminum oxide in calcium-vanadium-containing slag, spherical particles, vanadium iron ore and manganese ore respectively. The present invention preferably inputs the detection results into a computer, and the present invention uses a computer to determine the amount of calcium-vanadium-containing slag, spherical particles, vanadium iron ore and manganese ore through an automatic batching system according to the contents of vanadium, manganese, silicon and iron in the required low-vanadium manganese iron alloy material; then calculates the contents of calcium, magnesium, aluminum and phosphorus in the calcium-vanadium-containing slag, spherical particles, vanadium iron ore and manganese ore mixed materials to determine the pH of the mixed materials, calculates the amount of pH regulator to be added, and adjusts the pH to 0.8±0.2; finally calculates the amount of reducing agent to perform carbon reduction.

[0035] In the present invention, the mixing process preferably further includes: crushing and screening the vanadium iron ore and the manganese ore. The present invention has no special requirements for the crushing, and a conventional method in the art can be used. After the vanadium iron ore and the manganese ore are screened, the vanadium iron ore and the manganese ore are added in different particle sizes during the smelting process to control the air permeability during the smelting process and improve the recovery rate.

[0036] The present invention comprises the following steps of mixing calcium-vanadium-containing slag, spherical particles, vanadium iron ore, manganese ore, an iron source, a reducing agent and a pH regulator:

[0037] The calcium-vanadium-containing slag, the spherical particles, the vanadium iron ore and the manganese ore are first mixed to obtain a first mixture;

[0038] The pH regulator and the first mixture are mixed for a second time to adjust the pH to 0.8±0.2 to obtain a second mixture;

[0039] The reducing agent, the iron source and the second mixture are subjected to a third mixing.

[0040] In the present invention, the mixing is preferably carried out in a mixing bin.

[0041] In the present invention, the smelting is preferably carried out in a submerged arc furnace, the smelting temperature is preferably 1600-1700°C, more preferably 1650°C; the smelting time is preferably 180-220 minutes. The present invention preferably determines the iron-tapping time according to the furnace conditions, and the iron-tapping time can be extended if the furnace conditions permit.

[0042] The present invention preferably controls the secondary voltage and current by adjusting the gear position of the ore-fired furnace and the electrode insertion depth so that the furnace transformer power factor is greater than 83%.

[0043] The invention realizes the reuse of waste steel slag in the steelmaking process, effectively recovers iron, manganese and vanadium in the waste steel slag and reduces the production cost of low-vanadium manganese iron alloy materials, thereby forming a multi-component alloy. The preparation method provided by the invention provides a new channel for smelting multi-component alloys using steel plant waste slag in an electric arc furnace.

[0044] In the present invention, waste slag is preferably generated after the smelting, and the waste slag is preferably used as a cement additive or in the production of mineral wool.

[0045] Figure 1 Schematic diagram of the process for preparing low-vanadium manganese iron alloy materials.

[0046] The preparation method provided by the invention is simple and easy to operate, and reduces the production cost of the low-vanadium-manganese ferroalloy material under the premise of realizing the recycling of waste slag.

[0047] The present invention also provides a low-vanadium manganese iron alloy material prepared by the preparation method described in the above technical solution, comprising the following components in percentage by mass:

[0048]

[0049] Calculated by mass percentage, the low-vanadium manganese iron alloy material provided by the present invention includes 2-20% V, preferably 2-6%.

[0050] Calculated by mass percentage, the low-vanadium manganese iron alloy material provided by the present invention includes 3-40% Mn, preferably 3-30%.

[0051] Calculated by mass percentage, the low-vanadium-manganese-iron alloy material provided by the present invention comprises 2-15% Si, preferably 2-6%.

[0052] The low-vanadium-manganese ferroalloy material provided by the present invention includes the balance of iron and ferroalloy associated elements in terms of mass percentage. In the present invention, the ferroalloy associated elements are preferably sulfur, phosphorus, carbon, calcium, and magnesium.

[0053] The present invention also provides the use of the low-vanadium manganese iron alloy material described in the above technical solution in the preparation of vanadium-containing alloy steel.

[0054] In order to further illustrate the present invention, the technical solutions provided by the present invention are described in detail below in conjunction with embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0055] Example 1

[0056] Shizuishan Baoliyuan Special Alloy Co., Ltd. has successfully smelted qualified low-vanadium manganese ferroalloy materials with the following mass contents in a 15500KVA submerged arc furnace according to the preparation method provided by the present invention: V: 3.2%, Mn: 3.05%, Si: 2.98%, P: 1.75%, C: 2.4%, S: 0.02%, and the remainder is iron and trace amounts of ferroalloy associated elements such as phosphorus, carbon, calcium, and magnesium.

[0057] The specific preparation process is as follows: crushing the calcium-vanadium-containing slag and then screening it to obtain calcium-vanadium-containing slag with a particle size of greater than or equal to 5 mm and less than 30 mm, greater than or equal to 30 mm and less than 50 mm, greater than or equal to 50 mm and less than 80 mm, greater than or equal to 80 mm and less than or equal to 120 mm, and less than 5 mm, and stacking them separately;

[0058] Screening the vanadium-containing tailings to obtain vanadium-containing tailings with a particle size of 0 to 5 mm;

[0059] The calcium-vanadium-containing slag with a particle size of less than 5 mm, the vanadium-containing tailings with a particle size of 0 to 5 mm and the fully soluble resin binder are mixed and pressed into balls to obtain spherical particles with a diameter of 50 mm;

[0060] The contents of vanadium, iron, manganese, phosphorus, silicon dioxide, magnesium oxide, calcium oxide and aluminum oxide in calcium-vanadium-containing slag, spherical particles, vanadium-containing tailings, vanadium iron ore and manganese ore are tested, and the results are input into the computer. The specific dosage of calcium-vanadium-containing slag, spherical particles, vanadium-containing tailings, vanadium iron ore and manganese ore is calculated according to the contents of vanadium, manganese, silicon and iron in the required low-vanadium manganese ferroalloy materials, and the material ratio is carried out according to the required dosage using the computer's automatic feeding system. Then, the contents of calcium, magnesium, aluminum and phosphorus in the mixture of calcium-vanadium-containing slag, spherical particles, vanadium iron ore and manganese ore are calculated to determine the pH of the mixture, and the amount of pH regulator to be added is calculated to adjust the pH to 0.8±0.2; finally, the amount of reducing agent is calculated to carry out carbon reduction; the calcium-vanadium-containing slag, spherical particles, vanadium iron ore and manganese ore are first mixed to obtain a first mixture; the pH regulator and the first mixture are second mixed to adjust the pH to 0.8±0.2 to obtain a second mixture; the reducing agent, iron source and the second mixture are third mixed and then smelted in a submerged arc furnace at 1650±50°C for 200 minutes to obtain a low-vanadium manganese iron alloy material.

[0061] The method provided by the invention can be used to prepare low-vanadium manganese ferroalloy materials in batches in a short-process steel plant.

[0062] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. People can also obtain other embodiments based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A method for preparing a low-vanadium manganese ferroalloy material, comprising the following steps: The calcium-vanadium-containing slag is crushed and then sieved to obtain calcium-vanadium-containing slag with a particle size of 5 to 120 mm and calcium-vanadium-containing slag with a particle size of less than 5 mm; Screening the vanadium-containing tailings to obtain vanadium-containing tailings with a particle size of less than 5 mm; The calcium-vanadium-containing slag with a particle size of less than 5 mm, the vanadium-containing tailings with a particle size of less than 5 mm and a binder are mixed and pressed into balls to obtain spherical particles; The chemical components of calcium-vanadium-containing slag, vanadium-containing tailings, vanadium iron ore and manganese ore are detected, and the material dosage is calculated according to the detection results. According to the calculated results, the calcium-vanadium-containing slag with a particle size of 5 to 120 mm, spherical particles, vanadium iron ore, manganese ore, iron source, reducing agent and pH regulator are mixed and smelted to obtain low-vanadium manganese iron alloy material.

2. The preparation method according to claim 1, characterized in that: The iron source includes steel scraps, iron oxide scale or iron ore with an iron content greater than 55%; The pH regulator is one or more of silica, silicon slag and dolomite.

3. The preparation method according to claim 1, characterized in that: The mass percentage of manganese in the manganese ore is more than 45%, and the mass percentage of phosphorus is less than 0.08%.

4. The preparation method according to claim 1, characterized in that: The reducing agent is blue charcoal and / or coke; The thermal strength of the coke is >55.

5. The preparation method according to claim 4, characterized in that: When the reducing agent is blue charcoal and coke, the mass ratio of the coke to blue charcoal is 1:1 to 1:

3.

6. The preparation method according to claim 1, characterized in that: The smelting is carried out in a submerged arc furnace at a temperature of 1600-1700° C. and for a time of 180-220 minutes.

7. The preparation method according to claim 1, characterized in that: The diameter of the spherical particles is greater than 38 mm.

8. The preparation method according to claim 1 or 7, characterized in that: The mixing of calcium-vanadium-containing slag, spherical particles, vanadium iron ore, manganese ore, iron source, reducing agent and pH regulator comprises the following steps: The calcium-vanadium-containing slag, the spherical particles, the vanadium iron ore and the manganese ore are first mixed to obtain a first mixture; The pH regulator and the first mixture are mixed for a second time to adjust the pH to 0.8±0.2 to obtain a second mixture; The reducing agent, the iron source and the second mixture are subjected to a third mixing.

9. The preparation method according to claim 1, characterized in that: The amount of each material used in the process of mixing the calcium-vanadium-containing slag, spherical particles, vanadium iron ore, manganese ore, iron source, reducing agent and pH regulator is determined by a computer through an automatic batching system.

10. The preparation method according to claim 1, characterized in that: The mixing process also includes crushing and screening the vanadium iron ore and the manganese ore before smelting.

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