A fast-melting high yield manganese additive based on particle size regulation and its preparation and steelmaking application method

Abstract

The present application relates to the field of alloy additive, disclose a kind of based on particle size control's high yield of quick melting manganese additive and its preparation and steelmaking application method, the manganese additive with mass parts, raw material includes metal manganese powder or low-carbon ferromanganese powder 95.0~99.0 parts, fluxing modification component 1.0~3.0 parts, anti-oxidation binder 0.5~1.0 parts, the fluxing modification component is CaO-Al2O3-SiO2 ternary system.The present application first establishes the quantitative matching mechanism of manganese additive particle size and melting, yield, purity, and realizes quick melting, high yield, high purity, low cost, easy industrialization through ternary fluxing system and environmental protection binder cooperation, solves the long-standing manganese alloying pain point in industry.

Description

Technical Field

[0001] This invention relates to the field of alloy additives, specifically to a high-yield, fast-melting manganese additive based on particle size control, and its preparation and steelmaking application methods. Background Technology

[0002] Manganese, as an indispensable core alloying and deoxidizing element in the steelmaking industry, plays a crucial role throughout the entire steelmaking process and has a decisive impact on steel quality. In actual smelting, adding appropriate amounts of manganese can significantly improve the strength, toughness, and hardenability of steel, effectively improving its mechanical properties. It can also suppress the influence of harmful impurities in the steel, helping to produce high-quality steel that meets the needs of various industries. Currently, commonly used manganese additives in steelmaking mainly include electrolytic manganese powder, low-carbon ferromanganese powder, and high-carbon ferromanganese. Different types of additives are flexibly selected according to the requirements of the smelting process and the type of steel.

[0003] Although manganese additives are widely used, existing technologies still have many core defects in practical applications, which seriously restrict the improvement of smelting efficiency and steel quality. Specifically, these defects are manifested in the following four aspects: 1) Traditional block ferromanganese has a small specific surface area, resulting in a very limited contact area with molten steel. This leads to a higher melting temperature and a significantly longer melting time, which not only reduces smelting efficiency but also easily causes problems such as local unmelted areas and component segregation, affecting the uniformity of steel composition and thus causing fluctuations in steel performance.

[0004] 2) If the grinding force of manganese powder is insufficient or the particle size is too coarse, its dissolution kinetic rate in molten steel will be significantly slowed down. Some manganese powder will sink to the bottom due to gravity and will not melt, thus failing to fully participate in the metallurgical reaction. This directly leads to a low manganese yield, resulting in resource waste and increased production costs.

[0005] 3) Conversely, if the grinding force is too great and the particle size is too fine, the manganese powder is prone to oxidation and volatilization reactions in the high-temperature smelting environment. At the same time, it will also generate serious dust, which will not only cause a decrease in manganese yield, but also bring impurities and dust in the air into the molten steel, reduce the purity of the molten steel, and affect the quality of the final steel.

[0006] 4) More importantly, the industry has not yet established a quantitative matching mechanism between grinding intensity, particle size, melting temperature, manganese yield and steel purity. The regulation of each parameter lacks scientific basis, resulting in large fluctuations in smelting indicators, making it difficult to achieve stable control, which is not conducive to the large-scale production of high-quality steel.

[0007] Therefore, developing a new type of manganese additive is of great significance in the field of iron and steel smelting. Summary of the Invention

[0008] The present invention aims to provide a high-yield, fast-melting manganese additive based on particle size control, and its preparation and steelmaking application methods, in order to solve the problems of difficulty in simultaneously achieving particle size, melting temperature, yield, purity, and unsatisfactory stability in the use of manganese additives in the prior art.

[0009] To achieve the above objectives, the present invention adopts the following technical solution: a high-yield manganese additive based on particle size control, wherein, by mass, the raw materials include 95.0-99.0 parts of metallic manganese powder or low-carbon ferromanganese powder, 1.0-3.0 parts of fluxing modifier, and 0.5-1.0 parts of anti-oxidation binder, and the fluxing modifier is a CaO-Al2O3-SiO2 ternary system.

[0010] Preferably, as an improvement, the mass ratio of CaO, Al2O3, and SiO2 in the fluxing modification component is 4:3:2.

[0011] Preferably, as an improvement, the anti-oxidation adhesive is a water-based phenolic resin or a starch-based adhesive.

[0012] Preferably, as an improvement, a method for preparing a rapid-melting, high-yield manganese additive based on particle size control includes the following steps: Step S1, coarse crushing: crush the electrolytic manganese or low-carbon ferromanganese raw materials; Step S2, Grinding: Use a roller mill or ball mill to grind the powder to a D50 of 120-180 mesh, with 80-200 mesh particles accounting for ≥90%; Step S3, Low-temperature mixing: Mix the manganese-based powder, fluxing components, and anti-oxidation binder evenly at ≤120℃; Step S4, Compression molding: Pressing into columnar particles with a diameter of φ8-16mm under a pressure of 15-25MPa; Step S5, Cooling and Packaging: Packaging after cooling under inert gas protection.

[0013] Preferably, as an improvement, in step S1, the particle size of the crushed electrolytic manganese or low-carbon ferromanganese raw material is ≤5mm.

[0014] Preferably, as an improvement, in step S4, the bulk density after compression is ≥3.8 g / cm³. 3 .

[0015] Preferably, as an improvement, a method for applying a high-yield, fast-melting manganese additive based on particle size control in steelmaking is provided, wherein the additive is added at a temperature of 1550–1600°C.

[0016] Preferably, as an improvement, the additive is added in one go during the later stage of steel deoxidation or the alloying stage.

[0017] Preferably, as an improvement, the additive is added and stirred for 3-5 minutes to ensure uniform composition.

[0018] The principle and advantages of this solution are as follows: In practical applications, this technical solution comprehensively optimizes and upgrades the formulation and preparation process of manganese additives to address the problems existing in the use of existing technologies. In terms of formulation composition, the fluxing modifier serves as the core raw material, providing a stable manganese source. The low-carbon formulation avoids carbon increase in molten steel, making it suitable for high-quality steel smelting. The fluxing modifier innovatively adopts a ternary low-melting-point eutectic system, with a melting point significantly lower than the temperature of molten steel. On the one hand, this reduces the surface melting activation energy of manganese particles, accelerating wetting and dissolution; on the other hand, it can rapidly form low-melting-point composite inclusions with the manganese deoxidation product MnO, promoting flotation and removal. Furthermore, the ternary system can inhibit high-temperature agglomeration and oxidation of manganese particles, improving melting uniformity. This technical solution is the first to match the particle size of the ternary fluxing system with that of the manganese additive, achieving integrated rapid melting, deoxidation, and impurity removal. In terms of the preparation process, this technical solution achieves a dissolution-oxidation balance between the specific surface area and diffusion distance of the raw materials through precise particle size control. During the research and development process, it was found that excessively coarse particles resulted in slow dissolution, settling to the bottom without melting, and a yield of <85%; while excessively fine particles led to high-temperature oxidation, volatilization, and dust generation, resulting in a yield of <88%. Furthermore, in the preparation process, low-temperature mixing avoids raw material oxidation and ensures uniform dispersion of the flux and binder. Through parameter control during the pressing stage, a high bulk density reduces porosity and lowers the high-temperature oxidation rate.

[0019] This technical solution establishes for the first time a quantitative matching mechanism between manganese additive particle size and melting, yield, and purity. Through the synergy of a ternary flux system and an environmentally friendly binder, it achieves a comprehensive breakthrough in rapid melting, high yield, high purity, low cost, and easy industrialization, solving the long-standing pain point of manganese alloying in the industry.

[0020] The beneficial effects of this technical solution are as follows: 1. Rapid melting: The melting time is shortened by more than 40% compared to block ferromanganese, reducing the temperature drop of molten steel and energy consumption.

[0021] 2. High yield: Manganese yield >97%, which is 5-10 percentage points higher than the traditional method, and element loss is greatly reduced.

[0022] 3. High purity: Total oxygen content is reduced by more than 30%, and inclusions are small and dispersed, significantly improving the quality of steel.

[0023] 4. Stable and controllable: Establish a quantitative mechanism for grinding intensity, particle size and metallurgical properties to solve the problem of composition fluctuation.

[0024] 5. The equipment is industrially friendly, versatile, and simple in process, enabling large-scale production and adaptable to the entire process of converter / LF / RH / electric furnace. Detailed Implementation

[0025] The following detailed description provides further details on specific embodiments, but the embodiments of the present invention are not limited thereto. Unless otherwise specified, the technical means used in the following embodiments are conventional means well known to those skilled in the art; the experimental methods used are all conventional methods; and the materials and reagents used are all commercially available.

[0026] Overview of the plan: A high-yield, fast-melting manganese additive based on particle size control comprises, by mass, 95.0–99.0 parts of metallic manganese powder or low-carbon ferromanganese powder, 1.0–3.0 parts of fluxing modifier, and 0.5–1.0 parts of anti-oxidation binder.

[0027] The fluxing modifier is a ternary low-melting-point system of CaO-Al2O3-SiO2 with a mass ratio of CaO:Al2O3:SiO2=4:3:2; the anti-oxidation binder is a water-based phenolic resin or starch-based binder, free of harmful impurities such as sulfur (S) and phosphorus (P).

[0028] A method for preparing a high-yield, fast-melting manganese additive based on particle size control includes the following steps: Step S1, coarse crushing: crush the electrolytic manganese or low-carbon ferromanganese raw material to a particle size ≤5mm; Step S2, Precision Grinding: Use a roller mill or ball mill, control the grinding intensity, so that the powder D50 = 120-180 mesh, and the proportion of 80-200 mesh particles ≥ 90%; Step S3, Low-temperature mixing: Mix the manganese-based powder, fluxing component, and anti-oxidation binder at ≤120℃ for 10-20 minutes to disperse them evenly; Step S4, Compression Molding: The pellets are pressed into cylindrical shapes with a diameter of 8-16 mm under a pressure of 15-25 MPa, with a bulk density ≥ 3.8 g / cm³. 3 ; Step S5, Cooling and Packaging: Cooling with inert gas and sealing the packaging to prevent moisture absorption and oxidation.

[0029] A method for applying a high-yield, fast-melting manganese additive based on particle size control in steelmaking. The additive is suitable for the entire process of converter steelmaking, LF furnace refining, RH refining, and electric furnace steelmaking. The additive is added at a temperature of 1550–1600℃. The additive is added in one go during the later stage of steel deoxidation or alloying. After adding the additive, the mixture is stirred for 3–5 minutes to ensure uniform composition.

[0030] Example 1 A high-yield, rapidly melting manganese additive based on particle size control comprises, by mass percentage, 97.5% metallic manganese powder, 2.0% fluxing modifier, and 0.5% anti-oxidation binder. The fluxing modifier is a ternary low-melting-point system of CaO-Al2O3-SiO2 with a mass ratio of CaO:Al2O3:SiO2 = 4:3:2; the anti-oxidation binder is an aqueous phenolic resin.

[0031] A method for preparing a high-yield, fast-melting manganese additive based on particle size control includes the following steps: Step S1, coarse crushing: crush the electrolytic manganese or low-carbon ferromanganese raw material to a particle size ≤5mm; Step S2, Precision Grinding: Use a roller mill or ball mill to control the grinding intensity so that the powder D50 = 150 mesh, and the proportion of 80-200 mesh particles is 95%; Step S3, Low-temperature mixing: Mix the manganese-based powder, fluxing component, and anti-oxidation binder at ≤120℃ for 10-20 minutes to disperse them evenly; Step S4, Compression Molding: The pellets are compressed into φ12mm columnar granules under a pressure of 18MPa, with a bulk density ≥3.8g / cm³. 3 ; Step S5, Cooling and Packaging: Cooling with inert gas and sealing the packaging to prevent moisture absorption and oxidation.

[0032] A method for applying a high-yield, rapidly melting manganese additive based on particle size control in steelmaking, wherein the additive is added at a temperature of 1570℃.

[0033] Example 2 A high-yield, rapidly melting manganese additive based on particle size control comprises, by mass percentage: 96% low-carbon ferromanganese powder, 3.0% fluxing modifier, and 1.0% anti-oxidation binder. The fluxing modifier is a ternary low-melting-point system of CaO-Al2O3-SiO2 with a mass ratio of CaO:Al2O3:SiO2 = 4:3:2; the anti-oxidation binder is an aqueous phenolic resin.

[0034] A method for preparing a high-yield, fast-melting manganese additive based on particle size control includes the following steps: Step S1, coarse crushing: crush the electrolytic manganese or low-carbon ferromanganese raw material to a particle size ≤5mm; Step S2, Precision Grinding: Use a roller mill or ball mill to control the grinding intensity so that the powder D50 = 120 mesh, and the proportion of 80-200 mesh particles is 92%; Step S3, Low-temperature mixing: Mix the manganese-based powder, fluxing component, and anti-oxidation binder at ≤120℃ for 10-20 minutes to disperse them evenly; Step S4, Compression Molding: The pellets are compressed into φ10mm cylindrical shapes under a pressure of 20MPa, with a bulk density ≥3.8g / cm³. 3 ; Step S5, Cooling and Packaging: Cooling with inert gas and sealing the packaging to prevent moisture absorption and oxidation.

[0035] A method for applying a high-yield, rapidly melting manganese additive based on particle size control in steelmaking, wherein the additive is added at a temperature of 1560℃.

[0036] Example 3 A high-yield, fast-melting manganese additive based on particle size control comprises, by mass percentage, 99% metallic manganese powder, 1.0% fluxing modifier, and 0% anti-oxidation binder. The fluxing modifier is a ternary low-melting-point system of CaO-Al2O3-SiO2 with a mass ratio of CaO:Al2O3:SiO2 = 4:3:2.

[0037] A method for preparing a high-yield, fast-melting manganese additive based on particle size control includes the following steps: Step S1, coarse crushing: crush the electrolytic manganese or low-carbon ferromanganese raw material to a particle size ≤5mm; Step S2, Precision Grinding: Use a roller mill or ball mill to control the grinding intensity so that the powder D50 = 180 mesh, and the 80-200 mesh particle size accounts for 90%; Step S3, Low-temperature mixing: Mix the manganese-based powder, fluxing component, and anti-oxidation binder at ≤120℃ for 10-20 minutes to disperse them evenly; Step S4, Compression Molding: The pellets are compressed into φ16mm cylindrical shapes under a pressure of 25MPa, with a bulk density ≥3.8g / cm³. 3 ; Step S5, Cooling and Packaging: Cooling with inert gas and sealing the packaging to prevent moisture absorption and oxidation.

[0038] A method for applying a high-yield, rapidly melting manganese additive based on particle size control in steelmaking, wherein the additive is added at a temperature of 1590℃.

[0039] Comparative Example 1 The difference between this comparative example and Example 1 is that in this comparative example, conventional blocky ferromanganese is used as an additive.

[0040] Comparative Example 2 The difference between this comparative example and Example 1 is that in this comparative example, 95% of the manganese powder after precise grinding has a particle size <200 mesh.

[0041] Comparative Example 3 The difference between this comparative example and Example 1 is that in this comparative example, 95% of the manganese powder after precise grinding has a particle size >80 mesh.

[0042] Comparative Example 4 The difference between this comparative example and Example 1 is that the fluxing modification component in this comparative example is a ternary low-melting-point system of CaO-Al2O3-SiO2 with a mass ratio of CaO:Al2O3:SiO2=1:1:1.

[0043] Comparative Example 5 The difference between this comparative example and Example 1 is that the fluxing modification component in this comparative example is a binary low-melting-point system of CaO-SiO2 with a mass ratio of CaO:SiO2=2:1.

[0044] Comparative Example 6 The difference between this comparative example and Example 1 is that the fluxing modifier in this comparative example is SiO2.

[0045] The manganese additives prepared in the above embodiments and comparative examples were applied to steelmaking. The amount of additive added was 3.5 kg / t steel. The test indicators included additive melting time, manganese yield, total oxygen content in molten steel, and mechanical properties of steel (strength and impact toughness). The test methods are as follows: Additive melting time: recorded using traditional observation methods; Manganese recovery rate: (recovered amount / added amount) × 100%; Total oxygen content in molten steel: The test method refers to GB / T 11261-2022 "Determination of oxygen content in steel - pulse heating inert gas melting - infrared absorption method"; Hardness: The test method refers to GB / T 230.1-2018; Impact resistance: The test method is in accordance with GB / T 229-2020.

[0046] Each group underwent three repeated trials, and the test results are shown in Table 1: Table 1 Group Melting time (s) Harvest rate (%) Total oxygen content (ppm) Hardness HRC60 <![CDATA[Impact toughness J / cm 2 > Example 1 78 97.2 22.1 58 72 Example 2 75 98.1 20.7 59 74 Example 3 81 97.5 23.5 57 70 Comparative Example 1 135 86.6 34 52 58 Comparative Example 2 72 90.1 28.6 54 62 Comparative Example 3 118 87.5 31.2 53 59 Comparative Example 4 96 91.3 26.3 55 65 Comparative Example 5 102 90.2 27.5 54 63 Comparative Example 6 110 89.5 29.8 53 60 As shown in Table 1, the performance of the embodiment is significantly superior to that of traditional blocky ferromanganese, with faster melting, higher yield, purer molten steel, and better mechanical properties. Specifically, in the 80-200 mesh and D50=120-180 mesh range of this invention, the melting time is shortened by more than 40%, the manganese yield is >97%, and the total oxygen is reduced by ≥32%; both excessively fine and excessively coarse materials lead to a decrease in yield and a deterioration in purity. Regarding the fluxing system: the ternary system of this invention has the best fluxing and impurity removal; other ratios, binary or single components all significantly reduce melting speed, yield, and purity.

[0047] The above descriptions are merely embodiments of the present invention, and common knowledge such as specific technical solutions and / or characteristics are not described in detail here. It should be noted that those skilled in the art can make various modifications and improvements without departing from the technical solutions of the present invention, and these should also be considered within the scope of protection of the present invention. These modifications and improvements will not affect the effectiveness of the implementation of the present invention or the practicality of the patent. The scope of protection claimed in this application should be determined by the content of its claims, and the specific embodiments described in the specification can be used to interpret the content of the claims.

Claims

1. A high-yield, fast-melting manganese additive based on particle size control, characterized in that: By weight, the raw materials include 95.0 to 99.0 parts of metallic manganese powder or low-carbon ferromanganese powder, 1.0 to 3.0 parts of fluxing modifier, and 0.5 to 1.0 parts of anti-oxidation binder, wherein the fluxing modifier is a CaO-Al2O3-SiO2 ternary system.

2. The rapid-melting, high-yield manganese additive based on particle size control according to claim 1, characterized in that: The mass ratio of CaO, Al2O3, and SiO2 in the fluxing modification component is 4:3:

2.

3. The rapid-melting, high-yield manganese additive based on particle size control according to claim 2, characterized in that: The antioxidant adhesive is a water-based phenolic resin or a starch-based adhesive.

4. A method for preparing a high-yield, rapidly melting manganese additive based on particle size control according to any one of claims 1 to 3, characterized in that, Includes the following steps: Step S1, coarse crushing: crush the electrolytic manganese or low-carbon ferromanganese raw materials; Step S2, Grinding: Use a roller mill or ball mill to grind the powder to a D50 of 120-180 mesh, with 80-200 mesh particles accounting for ≥90%; Step S3, Low-temperature mixing: Mix the manganese-based powder, fluxing components, and anti-oxidation binder evenly at ≤120℃; Step S4, Compression molding: Pressing into columnar particles with a diameter of φ8-16mm under a pressure of 15-25MPa; Step S5, Cooling and Packaging: Packaging after cooling under inert gas protection.

5. The method for preparing a high-yield, rapidly melting manganese additive based on particle size control according to claim 4, characterized in that: In step S1, the particle size of the crushed electrolytic manganese or low-carbon ferromanganese raw material is ≤5mm.

6. The method for preparing a high-yield, fast-melting manganese additive based on particle size control according to claim 5, characterized in that: In step S4, the bulk density after compression is ≥3.8 g / cm³. 3 .

7. The method for applying a high-yield, fast-melting manganese additive based on particle size control in steelmaking, as described in any one of claims 1 to 3, is characterized in that: The additive is added at a temperature of 1550–1600℃.

8. The method for applying a high-yield, fast-melting manganese additive based on particle size control in steelmaking according to claim 7, characterized in that: The additives are added in a single step during the later stage of steel deoxidation or alloying.

9. The application method of a high-yield, fast-melting manganese additive based on particle size control in steelmaking according to claim 8, characterized in that: After adding the additive, stir for 3-5 minutes to ensure the ingredients are uniform.