CN112853042B - Method for increasing manganese in high manganese steel smelting process - Google Patents
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- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
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- C21C7/064—Dephosphorising; Desulfurising
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Abstract
The invention relates to a method for increasing manganese and removing manganese in the refining process of high manganese steelThe sulfur method comprises the steps of mixing manganese ore powder and aluminum powder to obtain mixed powder; in the process of smelting high manganese steel, the mixed powder is added into molten slag, manganese ore powder and aluminum powder are subjected to oxidation reaction by using the high temperature of the molten slag, and liquid manganese metal generated by the reaction directly settles to the liquid level of the molten steel and enters the molten steel, so that the manganese content in the molten steel is increased; the alumina is combined with calcium oxide in the slag to generate 12CaO 7Al 2 O 3 . The invention can achieve the aims of increasing manganese, desulfurizing and purifying molten steel in the process of smelting high manganese steel.
Description
Technical Field
The invention relates to the technical field of high manganese steel smelting, in particular to a method for increasing manganese in a high manganese steel smelting process.
Background
In the smelting process of manganese-containing steel, manganese is generally added into a smelting furnace in the form of ferromanganese alloy or metal manganese, electrolytic manganese and the like; for steel grades with low manganese content, the temperature loss caused in the manganese alloying process can be compensated by a method of chemically heating or physically heating molten steel. However, for steel grades with high manganese content (more than 10%), the method for simply heating molten steel brings two disadvantages:
1. if a physical temperature rise method is adopted, the temperature rise time is longer, for example, the LF furnace electrode temperature rise is taken as an example, the damage of steel ladle refractory materials can be aggravated due to long-time temperature rise, and meanwhile, the nitrogen content of molten steel is seriously increased, so that the molten steel components can not meet the requirements.
2. If a chemical temperature rise method is adopted, taking the example of adding aluminum and blowing oxygen for temperature rise, a large amount of alumina inclusions exist in the molten steel, and the cleanliness of the molten steel is not favorable.
Therefore, for the production of steel grades with higher manganese content, how to compensate the temperature loss caused by manganese alloying is a difficult problem in the smelting process.
The Chinese invention patent with the publication number CN105838848B discloses a preparation method of high manganese steel, which comprises the following steps: heating and melting scrap steel; introducing oxygen for 5-10 minutes, keeping the furnace temperature at more than 1550 ℃, and keeping the slag amount of the furnace slag at least 2%; removing part of slag, adding electrolytic manganese, pig iron, high-carbon ferromanganese and low-carbon ferrochromium, melting, and adding 60% of aluminum, 20% of silicon and 20% of calcium alloy of the total amount of molten steel for deoxidation; scattering composite powder of 1 percent of carbon, 50 percent of silicon and 49 percent of calcium in the total amount of the molten steel into the molten steel slag, keeping for 5 to 10 minutes, introducing heated and dehydrated argon, and keeping for 5 to 10 minutes; pouring molten steel into a baked steel ladle, presetting yttrium-based rare earth at the ladle bottom, solidifying and cooling at the tapping temperature of 1460-1500 ℃ and the pouring temperature of 1370-1390 ℃ to obtain the high manganese steel.
The Chinese invention patent with the publication number of CN105803322B discloses 'high manganese steel and a preparation method thereof', wherein the high manganese steel comprises the following components in percentage by mass: c:0.9 to 1.6%, mn:12 to 26%, cr:1.5 to 2.5%, ti:2.0 to 2.5%, W:4.0 to 5.0 percent of Fe, less than or equal to 0.04 percent of P, and the balance of Fe and inevitable impurities. The preparation method of the high manganese steel comprises the following steps: according to the component requirements, uniformly mixing carbon powder, electrolytic manganese powder, high-carbon manganese iron powder and high-carbon ferrochrome powder to obtain tungsten-titanium-containing high-manganese steel alloy powder, and keeping the mixture for 20 to 40 minutes under the pressure of 120 to 180MPa by using a cold isostatic pressing method to prepare a high-manganese steel blank; sintering the high manganese steel blank at 1300-1400 ℃ under the vacuum degree of 1-10 Pa, and cooling to obtain the high manganese steel.
The 2 methods in the above patent documents can increase the manganese content in the steel, but both of them have two problems: firstly, the raw materials such as electrolytic manganese are used, and the cost is high. Secondly, when manganese is alloyed, both molten steel desulfurization and molten steel purification cannot be considered.
Disclosure of Invention
The invention provides a method for increasing manganese in a high manganese steel smelting process, which can achieve the purposes of increasing manganese, desulfurizing and purifying molten steel in the high manganese steel smelting process.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for increasing manganese in the smelting process of high manganese steel is provided, manganese ore powder and aluminum powder are mixed to obtain mixed powder; in the process of smelting high manganese steel, the mixed powder is added into molten slag, manganese ore powder and aluminum powder are subjected to oxidation reaction by using the high temperature of the molten slag, and liquid manganese metal generated by the reaction directly settles to the liquid level of the molten steel and enters the molten steel, so that the manganese content in the molten steel is increased; the alumina is combined with calcium oxide in the slag to generate 12CaO 7Al 2 O 3 。
A method for increasing manganese and desulfurizing in a high manganese steel smelting process specifically comprises the following steps:
(1) Calculating the dosage of the mixed powder according to the liquid steel quantity of the high manganese steel and the requirement of manganese components; according to MnO, feO and SiO in manganese ore powder 2 The mass content of the manganese ore powder and the aluminum powder is calculated, and the calculation process is as follows:
a) Calculating the quality Q of manganese in molten steel Mn ：
Q Mn ＝Q×W Mn
In the formula: q is total mass of molten steel, W Mn The percentage content of manganese in the molten steel;
b) Calculating the mass Q of manganese ore powder required by increasing manganese Manganese ore ：
Q Manganese ore ＝Q Mn ÷(W MnO ÷A)
In the formula: w MnO The mass percentage of MnO in the manganese ore is; a is the atomic weight percentage content of Mn in MnO molecules;
c) Calculating the quality Q of the aluminum powder Aluminum powder ：
Q Aluminum powder ＝k×(0.25×W MnO +0.25×W FeO +0.9×W SiO2 )×Q Manganese ore
In the formula, the coefficient k is the loss of the reaction of the aluminum powder and air, and k = 1.1-1.3; w FeO The mass percentage of FeO in the mineral powder; w SiO2 Is SiO in mineral powder 2 The mass percentage of (A);
d) Calculating the mass Q of the mixed powder:
Q＝Q manganese ore +Q Aluminum powder
(2) Mixing manganese ore powder with aluminum powder according to the calculation result of the step (1) to obtain mixed powder;
(3) In the process of smelting high manganese steel, the mixed powder is added to the molten slag, and argon is blown in the process of adding and stirring;
(4) Detecting the manganese content in the molten steel after slagging off, and if the manganese content is insufficient, adjusting by using a ferromanganese alloy to ensure that the manganese content meets the requirement of high manganese steel components;
(5) And adjusting other chemical components and temperature of the molten steel until the smelting process is finished.
The mixed powder is packaged in bags by sealing bags; in the process of smelting high manganese steel, the bagged mixed powder is added to the molten slag through a feeding system.
In the step (3), the flow of bottom-blown argon is 0.20-0.35 m 3 Per ton of steel.
Compared with the prior art, the invention has the beneficial effects that:
1) The molten steel is directly alloyed by manganese ore, so that the manufacturing procedures of ferroalloy are reduced;
2) The functions of slag desulfurization and inclusion adsorption in the molten steel are added while the manganese is added to the molten steel;
3) The comprehensive efficiency of manganese increasing, desulfurizing and purifying the molten steel is high, and the high manganese molten steel with low sulfur and high purity can be obtained.
Detailed Description
The invention relates to a method for increasing manganese and desulfurizing in a high manganese steel smelting process, which comprises the steps of mixing manganese ore powder and aluminum powder to obtain mixed powder; in the process of smelting high manganese steel, the mixed powder is added into slag, the manganese ore powder and the aluminum powder are subjected to oxidation reaction by using the high temperature of the slag, and the liquid manganese metal generated by the reaction is directly settled to the liquid level of the molten steel and enters the molten steel, so that the manganese content in the molten steel is increased; the alumina is combined with the calcium oxide in the slag to generate 12CaO 7Al 2 O 3 。
A method for increasing manganese and desulfurizing in a high manganese steel smelting process specifically comprises the following steps:
(1) Calculating the dosage of the mixed powder according to the liquid steel quantity of the high manganese steel and the requirement of manganese components; according to MnO, feO and SiO in manganese ore powder 2 The mass content of the manganese ore powder and the aluminum powder is calculated, and the calculation process is as follows:
a) Calculating the quality Q of manganese in molten steel Mn ：
Q Mn ＝Q×W Mn
In the formula: q is the total mass of molten steel, W Mn Is the percentage content of manganese in the molten steel;
b) Calculating the mass Q of manganese ore powder required by increasing manganese Manganese ore ：
Q Manganese ore ＝Q Mn ÷(W MnO ÷A)
In the formula: w MnO The mass percentage of MnO in the manganese ore is; a is the atomic weight percentage content of Mn in MnO molecules;
c) Calculating the quality Q of the aluminum powder Aluminum powder ：
Q Aluminum powder ＝k×(0.25×W MnO +0.25×W FeO +0.9×W SiO2 )×Q Manganese ore
In the formula, the coefficient k is the loss of the reaction of aluminum powder and air, and k = 1.1-1.3; w FeO The mass percentage of FeO in the mineral powder; w SiO2 Is SiO in mineral powder 2 The mass percentage of (A);
d) Calculating the mass Q of the mixed powder:
q = Q manganese ore + Q aluminum powder
(2) Mixing manganese ore powder with aluminum powder according to the calculation result of the step (1) to obtain mixed powder;
(3) In the process of smelting high manganese steel, the mixed powder is added to the molten slag, and argon is blown in the process of adding and stirring;
(4) Detecting the manganese content in the molten steel after slagging off, and if the manganese content is insufficient, adjusting by using a ferromanganese alloy to ensure that the manganese content meets the requirement of high manganese steel components;
(5) And adjusting other chemical components and temperature of the molten steel until the smelting process is finished.
The mixed powder is packaged in bags by sealing bags; in the process of smelting high manganese steel, the bagged mixed powder is added to the molten slag through a feeding system.
In the step (3), the flow of bottom-blown argon is 0.20-0.35 m 3 Per ton of steel.
The working principle of the method for increasing manganese and desulfurizing in the high manganese steel smelting process is as follows: mixing manganese ore powder and aluminum powder according to a certain proportion to obtain mixed powder, and adding the mixed powder to molten slag in the process of smelting high manganese steel; manganese oxide in manganese ore powder is used as an oxidizing agent, and aluminum powder is used as a reducing agent. The slag and the slag are oxidized at high temperature to release a large amount of heat (the heat quantity delta H = -259.58 KJ/molAl); the temperature of the slag is greatly increased, and reaction products including liquid metal manganese, aluminum oxide, a small amount of silicon oxide and the like are obtained. Wherein the liquid manganese metal directly settles to the liquid level of the molten steel and enters the molten steel, so that the manganese content in the molten steel is increased; alumina and calcium oxide in slag are combined into heptaaluminum dodecacalcium (12 CaO 7 Al) 2 O 3 ) The components with low melting point and high sulfur capacity absorb Al in the molten steel while deeply desulfurizing the molten steel 2 O 3 And the like; finally, the purposes of increasing manganese, desulfurizing and purifying molten steel are achieved.
The reaction formula of the oxidation reaction is:
Al+3/2MnO＝3/2Mn+1/2Al 2 O 3
the following examples are carried out on the premise of the technical scheme of the invention, and detailed embodiments and specific operation processes are given, but the scope of the invention is not limited to the following examples. The methods used in the following examples are conventional methods unless otherwise specified.
[ example 1 ]
In the embodiment, the manganese increasing and the desulfurization are realized in the process of smelting ZGMn13-4 steel in an electric arc furnace.
The amount of molten steel was 100 tons.
In the standard chemical components of ZGMn13-4 steel, the contents of carbon, manganese and sulfur are respectively as follows: [C] 0.90% -1.3%; 11.0 to 14.0 percent of Mn and less than or equal to 0.04 percent of S.
Main chemical composition of manganese ore powderThe weight contents are as follows: [ MnO ] of]:75.38％，[SiO 2 ]:3.11％，[FeO]16.77 percent. Manganese content =75.38% × 55/(55 + 16) =58.39%.
The specific process is as follows:
1. calculating the dosage of the mixed powder according to the liquid amount of the steel and the requirement of the manganese component of the high manganese steel;
and (3) calculating: the quality Q of manganese element required by 100 tons of ZGMn13-4 molten steel Mn =100 × 12.5% =12.5 tons (12.5% is an intermediate value of 11.0% to 14.0%); reducing 12.5 tons of manganese from manganese ore fines requires the mass of manganese ore fines: q Manganese ore =12.5/75.38%/54.26% =30.56 ton;
quality Q of required aluminum powder Aluminum powder ＝k×(0.25×W MnO +0.25×W FeO +0.9×W SiO2 )×Q Manganese ore =1.20 × (0.25 × 75.38% × 30.56+0.25 × 3.11% × 30.56+0.9 × 16.77% × 30.56) =12.7 tons;
the required mixed powder dosage is Q = Q Manganese ore +Q Aluminum powder =30.56+12.7=43.26 ton;
mixing manganese ore powder with aluminum powder to obtain mixed powder, and packaging the mixed powder in sealed bags (50 kg/bag);
2. in the process of smelting high manganese steel in an electric arc furnace, the bagged mixed powder is added to the molten slag through a feeding system. The addition rate was adjusted to 1.5 tons/min depending on the intensity of the reaction. In the process, large-flow argon bottom blowing stirring is carried out;
3. removing excessive slag;
4. 9.5 percent of Mn and 0.004 percent of S in the molten steel are detected, and the part with insufficient manganese components is adjusted by medium-carbon ferromanganese alloy, so that the content meets the requirement;
5. continuously adjusting other components and temperature until the requirements of smelting processes are met;
6. sampling and detecting, and the purity index T [ O ] in steel is 0.0010%. The high manganese steel liquid with low sulfur and high purity is obtained.
[ example 2 ]
In the embodiment, the manganese increasing and the desulfuration are realized in the process of smelting ZGMn13-1 steel in an electric arc furnace.
The amount of molten steel was 70 tons.
In the standard chemical components of ZGMn13-1 steel, the contents of carbon, manganese and sulfur are respectively as follows: [C] 1.0 percent to 1.45 percent; 11.0 to 14.0 percent of [ Mn ] and less than or equal to 0.04 percent of [ S ].
The manganese ore powder comprises the following main chemical components in percentage by mass: [ MnO ] of]:70.05％，[SiO 2 ]:3.41％，[FeO]15.56 percent, manganese content =70.05 percent multiplied by 55/(55 + 16) =54.26 percent.
The specific process is as follows:
1. calculating the dosage of the mixed powder according to the liquid amount of the steel and the requirement of the manganese component of the high manganese steel;
and (3) calculating: the quality Q of manganese element required by 70 tons of ZGMn13-1 molten steel Mn =70 × 12.5% =8.75 tons (12.5% is an intermediate value of 11.0% to 14.0%); reduction of 8.75 tons of manganese from manganese ore fines requires the mass Q of the manganese ore fines Manganese ore =8.75/70.05%/54.26% =23.02 ton;
quality Q of required aluminum powder Aluminum powder ＝k×(0.25×W MnO +0.25×W FeO +0.9×W SiO2 )×Q Manganese ore =1.20 x (0.25 x 70.05% × 23.02+0.25 x 3.41% × 23.02+0.9 x 15.56% × 23.02) =8.94 ton;
the required mixed powder dosage is Q = Q Manganese ore +Q Aluminum powder =23.02+8.94=31.96 ton.
The manganese ore powder and the aluminum powder are mixed to obtain mixed powder, and the mixed powder is packaged in sealed bags (100 kg/bag).
2. In the process of smelting high manganese steel in an electric arc furnace, the bagged mixed powder is added to the molten slag through a feeding system, and the adding speed is adjusted to be 1.0 ton/min according to the reaction strength. In the process, large-flow argon bottom blowing stirring is carried out;
3. removing excessive slag;
4. 9.8 percent of Mn and 0.0045 percent of S in the molten steel are detected, and the part with insufficient manganese is adjusted by medium carbon ferromanganese alloy, so that the content meets the requirement;
5. continuously adjusting other components and temperature until the requirements of smelting procedures are met;
6. sampling and detecting, and the index T [ O ] representing purity in steel is 0.0014%. The high manganese steel liquid with low sulfur and high purity is obtained.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (1)
1. A method for increasing manganese in the smelting process of high manganese steel is characterized in that manganese ore powder and aluminum powder are mixed to obtain mixed powder; in the process of smelting high manganese steel, the mixed powder is added into molten slag, manganese ore powder and aluminum powder are subjected to oxidation reaction by using the high temperature of the molten slag, and liquid manganese metal generated by the reaction directly settles to the liquid level of the molten steel and enters the molten steel, so that the manganese content in the molten steel is increased; the alumina is combined with the calcium oxide in the slag to generate 12CaO 7Al 2 O 3 (ii) a The mixed powder is packaged in bags by sealing bags; in the process of smelting high manganese steel, adding the bagged mixed powder to molten slag through a charging system;
the method specifically comprises the following steps:
(1) Calculating the dosage of the mixed powder according to the liquid steel quantity of the high manganese steel and the requirement of manganese components; according to MnO, feO and SiO in manganese ore powder 2 The mass content of the manganese ore powder and the aluminum powder is calculated, and the calculation process is as follows:
a) Calculating the quality Q of manganese in molten steel Mn ：
Q Mn ＝Q×W Mn
In the formula: q is total mass of molten steel, W Mn Is the percentage content of manganese in the molten steel;
b) Calculating the mass Q of manganese ore powder required by increasing manganese Manganese ore ：
Q Manganese ore ＝Q Mn ÷(W MnO ÷A)
In the formula: w is a group of MnO The mass percentage of MnO in the manganese ore is; a is the atomic weight percentage content of Mn in MnO molecules;
c) Calculating the quality Q of the aluminum powder Aluminum powder ：
Q Aluminum powder ＝k×(0.25×W MnO +0.25×W FeO +0.9×W SiO2 )×Q Manganese ore
In the formula, the coefficient k is the loss of the reaction of the aluminum powder and air, and k = 1.1-1.3; w FeO The mass percentage of FeO in the mineral powder; w SiO2 Is SiO in mineral powder 2 The mass percentage of (A);
d) Calculating the mass Q of the mixed powder:
Q＝Q manganese ore +Q Aluminum powder
(2) Mixing manganese ore powder with aluminum powder according to the calculation result of the step (1) to obtain mixed powder;
(3) In the process of smelting high manganese steel, the mixed powder is added to the molten slag, and argon is blown in the process of adding and stirring; the flow of bottom-blown argon is 0.20-0.35 m 3 Per hour of steel;
(4) Detecting the manganese content in the molten steel after slagging off, and if the manganese content is insufficient, adjusting by using a ferromanganese alloy to ensure that the manganese content meets the requirement of high manganese steel components;
(5) And adjusting other chemical components and temperature of the molten steel until the smelting process is finished.
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