CN1524969A - Melted iron dephosphorization agent using vessel slag as raw material - Google Patents

Melted iron dephosphorization agent using vessel slag as raw material Download PDF

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CN1524969A
CN1524969A CNA031155766A CN03115576A CN1524969A CN 1524969 A CN1524969 A CN 1524969A CN A031155766 A CNA031155766 A CN A031155766A CN 03115576 A CN03115576 A CN 03115576A CN 1524969 A CN1524969 A CN 1524969A
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molten iron
slag
dephosphorization
converter slag
raw material
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CN1229506C (en
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陈兆平
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Baoshan Iron and Steel Co Ltd
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Baoshan Iron and Steel Co Ltd
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Abstract

A molten iron dephosphorization agent using furnace slag as raw material comprising the constituents of (wt%) furnace slag 20-50, calcarea lime 15-28, ferrum oxide 20-43, fluorite 0-3, soda 0-3, lime stone 0-3. The furnace slag proportion amounts 20-50%, the ferrum oxide can be sintered ore or rolled steel iron sheet, or can be revolving furnace smoke or sintered dedusting ash. The invention realizes reduced production costs, saved lime and low fusing point.

Description

Molten iron dephosphorization agent using converter slag as raw material
Technical Field
The invention relates to the technical field of pyrometallurgy, in particular to molten iron powder injection dephosphorization pretreatment of a torpedo ladle or a foundry ladle.
Background
Phosphorus is a harmful elementin most steel grades. In recent years, with the rapid development of science and technology, the requirements of users on the quality of steel are increasing. For example, low-temperature steel, marine steel, hydrogen-induced crack resistant steel, and steel for partial thick plates are required to have a phosphorus content of<0.01% or 0.005% in addition to an extremely low sulfur content. In addition, in order to reduce the production cost of oxygen converter steel and implement low-slag steel making, the phosphorus content of molten iron is required to be less than 0.015 percent. Therefore, many metallurgists devoted to the study on the pretreatment problem of the molten iron "three-step separation" since the 80 s have developed various treatment methods. Depending on the container used, two categories can be distinguished: one is dephosphorization in a ladle or torpedo ladle type hot metal mixer car containing molten iron; the other method is to carry out molten iron dephosphorization pretreatment in a converter. Both of these methods are industrially practically used.
The 'three-step' pretreatment of molten iron is a technology developed for producing high-purity steel, and the central problem is dephosphorization. The process is reasonably realized as follows: according to thermodynamic analysis, the temperature of the molten iron is lower than that of the molten steel, so that dephosphorization is facilitated, the carbon content in the molten iron is high, the activity of phosphorus is increased, and dephosphorization is facilitated; from the kinetic analysis, the decarburization reaction does not easily occur and the dephosphorization reaction easily occurs at the slag-iron interface, the lower the temperature is.
The lime slag system and the soda slag system are two types of molten iron dephosphorization agents which are industrially applied at present. The soda slag system can simultaneously dephosphorize and desulfurize the molten iron, but the high cost of the soda ash causes the problems of great reduction of the temperature of the molten iron, corrosion to refractory materials, a series of environmental pollution and the like, and is limited to a certain extent.
Therefore, the application of lime-based dephosphorizing agents composed of lime, fluorite, iron oxide, and the like is common at present. However, the dephosphorizing agent has the following problems in practical application:
(1) the initial slagging speed is slow, and the splashing is easy to occur in the blowing treatment;
(2) the dephosphorizing agent generally contains 6-15% of fluorite, has serious erosion to refractory materials, and fluoride in the dephosphorizing slag pollutes soil and is not beneficial to environmental protection;
(3) the cost of the dephosphorizing agent is high;
(4) the dephosphorization final slag has high free CaO, which is not beneficial to the comprehensive utilization of the dephosphorization slag.
Disclosure of Invention
The invention aims to provide the environment-friendly molten iron dephosphorization agent taking the converter slag as the raw material, which not only can greatly reduce the cost of the dephosphorization agent, but also can reduce the content of fluoride and free CaO in the dephosphorization slag, is beneficial to further utilization of the dephosphorization slag, simultaneously reduces the total slag amount in steelmaking and is beneficial to environmental protection.
The main components of the converter slag are calcium silicate, calcium ferrite and other oxides of iron, manganese, calcium and magnesium. After most converter slag is treated to eliminate the expansion and collapsefactors caused by f.CaO, the converter slag can be used as landfill material, road material, building material, such as wall material of steel slag cement, steel slag brick, etc., steel slag fertilizer, etc., and in addition, because the converter slag contains CaO and FeO, the converter slag can be returned to the blast furnace as part of raw materials and sintered for recycling.
The dephosphorization capability of the converter slag is analyzed, and the difference between the actual value and the calculated value of the distribution ratio of the phosphorus in the final slag of the converter is found, namely, the dephosphorization capability of the converter slag is not fully exerted, and the phosphorus is not balanced among slag metals. The main reasons are that slagging in the initial stage of blowing is not optimized, the amount of slag is excessive, and dynamic conditions are insufficient. Because the pretreatment temperature of the molten iron is 1300-1400 ℃ which is obviously lower than the blowing end temperature (about 1650 ℃) of the converter, the slag has larger dephosphorization capability at the molten iron temperature. Therefore, based on the dephosphorization capability of the converter slag and the characteristic that the converter slag is pre-melted, the dephosphorization agent can be completely used as a molten iron dephosphorization agent to replace lime, iron oxide and other components in the conventional lime slag dephosphorization agent.
In order to achieve the aim, the molten iron dephosphorization agent disclosed by the invention comprises the following components:
20-50 of converter slag
15-28 of lime
20-43 of iron oxide
The above are weight percentages.
The molten iron dephosphorization agent of the invention further comprises one or more than one offluorite, soda and limestone, which respectively account for the total weight percentage of the molten iron dephosphorization agent,
fluorite is more than 0 and less than or equal to 3
0 is more than soda and less than or equal to 3
Limestone is more than 0 and less than or equal to 3.
The converter slag can be conventional steelmaking converter slag or decarburization slag for smelting dephosphorization molten iron, and has the functions of both lime and iron oxide;
lime as an alkaline agent of dephosphorization agentThe active CaO exists in the form of ferrite, and after the high-activity CaO is rapidly dissolved, the high-activity CaO is mixed with P in the slag2O5Formation of 3CaO.P2O5；
The iron oxide is an oxidant, provides a solid oxygen source for the oxidation of P and simultaneously contributes to the melting of lime; the iron oxide is FeO and Fe2O3Or FeO, Fe2O3Any one of the above; the iron oxide can be sintered ore or steel sheet, and can also be converter smoke dust or sintering dedusting ash.
Fluorite is taken as a fluxing agent, so that the melting speed of lime is improved;
the soda can simultaneously dephosphorize and desulfurize, and can improve the dephosphorization capability of the lime series dephosphorization agent;
CaCO can be generated from limestone at molten iron temperature3Decomposition reaction of (1), (b) ) The heat absorption reduces the temperature of a reaction interface, which is beneficial to the dephosphorization reaction;
the converter slag is prepared from CaO and SiO2、MnO、FeO、Fe2O3、MgO、Al2O3、P2O5S, and the like; wherein the converter slag contains CaO/SiO22.0 to 4.5 of P2O5Less than or equal to 2.5 percent; the CaO content in the lime is more than or equal to 85 percent; the content of ferric oxide in the iron oxide is more than or equal to 70 percent; na in the soda2CO3The content is more than or equal to 95 percent; CaF in fluorite2The content is more than or equal to 85 percent.
The molten iron powder injection dephosphorization requires that converter slag, lime, iron oxide, fluorite, soda, limestone and the like are ground and uniformly stirred, and the method can be applied to molten iron powder injection dephosphorization pretreatment of a torpedo ladle or a foundry ladle.
The invention has the beneficial effects that:
compared with the dephosphorizing agent in the prior art, the invention has the following advantages:
(1) the proportion of the converter slag in the dephosphorizing agent reaches 20-50%, so that the production cost is obviously reduced;
(2) when 1kg/t.p converter slag is used, 0.5kg/t.p of lime can be saved;
(3) the dephosphorization agent has a desulfurization rate of more than 20 percent in the dephosphorization process;
(4) the dephosphorizing agent has low melting point and can form slag rapidly at lower temperature;
(5) in the dephosphorizing agent, lime exists in a high-activity CaO form, and a dephosphorized product is stable calcium phosphate, so that a rephosphorization reaction of later steelmaking is avoided;
(6) the occurrence rate of splashing in the process of powder spraying treatment is obviously reduced;
(7) the content of free CaO in the dephosphorized final slag is obviously reduced and is below 1 percent;
(8) the proportion of fluorite in the dephosphorizing agent is low and is less than or equal to 3 percent, so that the corrosion of the dephosphorizing agent to the torpedo ladle refractory material is reduced; meanwhile, the content of F in the final dephosphorization slag is obviously reduced to be below 1 percent, which is beneficial to environmental protection;
(9) the dephosphorizing agent is made of waste converter slag, has low cost, is beneficial to environmental protection and reduces the total slag amount of steel making.
Detailed Description
Table 1 shows examples of the present invention. Table 2 shows comparative examples.
TABLE 1
Molten iron dephosphorizing agent component (weight percentage)
Converter slag Lime Iron oxide Fluorite (Fluorite) Soda ash Limestone
Example 1 20 28 43 3 3 3
Example 2 50 18 26 2 2 2
Example 3 20 28 43 3 3 3
Example 4 40 22 30 3 3 2
Example 5 28 30 42 0 0 0
Example 6 40 24 33 3 0 0
Example 7 28 30 40 0 0 2
Example 8 30 30 38 0 2 0
TABLE 2
Conventional dephosphorizing agent (percentage by weight)
Sintered ore Lime CaF2
Comparative example 54 38 8
Example 1
Example 1 composition of molten iron dephosphorizing agent is shown in table 1. 100kg of molten iron is charged into a 250kg induction furnace,spraying powder at 1400 deg.C, and blowing N2Gas or Ar gas; the blowing pressure is 0.2-0.3 Mpa, and the gas flow is 0.4-0.5 Nm3And h, blowing 4kg of molten iron dephosphorization agent at the powder blowing speed of 200-800 g/min.
The results of the dephosphorization agent for molten iron of example 1 of the present invention, compared with the comparative examples, are shown in Table 3.
TABLE 3
Pretreatment Components (%) Treated Components (%) ηP (％) ηS (％)
Si P S P S
Example 1 0.20 0.088 0.027 0.040 0.018 54.5 33.3
Comparative example 0.20 0.078 0.025 0.041 0.019 47.4 24.0
Example 2
Example 2 composition of molten iron dephosphorizing agent is shown in table 1. Charging molten iron 100kg into an induction furnace of 250kg, performing powder spraying treatment at 1350 ℃, and spraying N2Gas or Ar gas; the blowing pressure is 0.2-0.3 Mpa, and the gas flow is 0.4-0.5 Nm3And h, blowing 4kg of dephosphorizing agent at the powder blowing speed of 200-800 g/min.
The dephosphorization agent for molten iron of this example was compared with the conventional dephosphorization agent, and the results are shown in Table 4.
TABLE 4
The components before treatment% The components after treatment are% ηP ％ ηS ％
Si P S P S
Example 2 0.06 0.086 0.019 0.026 0.011 69.8 42.1
Comparative example 0.06 0.074 0.022 0.032 0.014 56.8 36.4
Example 3
Example 3 composition of molten iron dephosphorizing agent is shown in table 1. Carrying out molten iron pretreatment in a 320-ton torpedo ladle, wherein the molten iron dephosphorization temperature is 1300-1400 ℃;
the dephosphorization agent for molten iron of this example was compared with the conventional dephosphorization agent, and the results are shown in Table 5.
TABLE 5
Time of day The components before treatment% After being processed intoIn percent Treatment of Time of day min Temperature reduction ℃ ηP ％ ηS ％
Si P S P S
Example 3 0.14 0.080 0.029 0.026 0.003 34 116.8 67.5 89.7
Comparative example 0.11 0.072 0.026 0.024 0.003 33.2 128.3 66.7 88.5
Example 4
Example 4 composition of molten iron dephosphorizing agent is shown in table 1.
The pretreatment of molten iron was carried out in a 320-ton torpedo ladle under the same test conditions as in example 3.
The dephosphorization agent for molten iron of this example was compared with the conventional dephosphorization agent, and the results are shown in Table 6.
TABLE 6
Time of day The components before treatment% The components after treatment are% Treatment of Time of day min Temperature reduction ℃ ηP ％ ηS ％
Si P S P S
Example 4 0.07 0.073 0.032 0.017 0.002 24.4 117.2 76.7 93.8
Comparative example 0.08 0.072 0.026 0.022 0.003 25.2 122.3 69.4 88.5
Example 5
Example 5 composition of molten iron dephosphorizing agent is shown in table 1. 100kg of molten iron is charged into a 250kg induction furnace,spraying powder at 1350 deg.C, and blowing N2Gas or Ar gas; the blowing pressure is 0.2-0.3 Mpa, and the gas flow is 0.4-0.5 Nm3And h, blowing 4kg of dephosphorizing agent at the powder blowing speed of 200-800 g/min.
The dephosphorization agent for molten iron of this example was compared with the conventional dephosphorization agent, and the results are shown in Table 7.
TABLE 7
Pretreatment Components (%) Treated Components (%) ηP (％) ηS (％)
Si P S P S
Example 5 0.04 0.080 0.018 0.029 0.010 63.8 44.4
Comparative example 0.06 0.074 0.022 0.032 0.014 56.8 36.4
Example 6
Example 6 composition of molten iron dephosphorizing agent is shown in table 1. Charging 100kg molten iron into a 250kg induction furnace, performing powder spraying treatment at 1400 ℃, and spraying N2Gas or Ar gas; the blowing pressure is 0.2-0.3 Mpa, and the gas flow is 0.4-0.5 Nm3And h, blowing 4kg of molten iron dephosphorization agent at the powder blowing speed of 200-800 g/min.
The results of the dephosphorization agent for molten iron of example 6 of the present invention, compared with the comparative examples, are shown in Table 8.
TABLE 8
Pretreatment Components (%) Treated Components (%) ηP (％) ηS (％)
Si P S P S
Example 6 0.18 0.083 0.022 0.035 0.014 57.8 36.4
Comparative example 0.20 0.088 0.027 0.040 0.018 54.5 33.3
Example 7
Example 7 composition of molten iron dephosphorizing agent is shown in Table 1. Carrying out molten iron pretreatment in a 320-ton torpedo ladle, wherein the molten iron dephosphorization temperature is 1300-1400 ℃;
the dephosphorization agent for molten iron of this example was compared with the conventional dephosphorization agent, and the results are shown in Table 9.
TABLE 9
The components before treatment% The components after treatment are% Treatment of Time of day min Temperature reduction ℃ ηP ％ ηS ％
Si P S P S
Example 7 0.12 0.078 0.030 0.023 0.003 32.6 115.2 70.5 90.0
Comparative example 0.11 0.072 0.026 0.024 0.003 33.2 128.3 66.7 88.5
Example 8
Example 8 the composition of the molten iron dephosphorizing agent is shown in Table 1.
And (3) pretreating molten iron in a 320-ton torpedo ladle, wherein the dephosphorization temperature range of the molten iron is 1300-1400 ℃.
The dephosphorization agent for molten iron of this example was compared with the conventional dephosphorization agent, and the results are shown in Table 10.
Watch 10
The components before treatment% The components after treatment are% Treatment of Time of day min Temperature reduction ℃ ηP ％ ηS ％
Si P S P S
Example 8 0.06 0.076 0.029 0.018 0.003 24.9 119.2 76.3 89.7
Comparative example 0.08 0.072 0.026 0.022 0.003 25.2 122.3 69.4 88.5
The molten iron dephosphorization agent which takes the converter slag as the raw material is used for treating more than 10 ten thousand tons of molten iron, and the production practice results show that: the dephosphorization effect (dephosphorization rate, unit consumption, time and the like) of the molten iron dephosphorization agent taking the converter slag as the raw material is equivalent to that of the conventional dephosphorization agent, the treatment temperature drop is reduced, the cost of each ton of the dephosphorization agent is reduced by more than 100 yuan, the pulverization of the pretreated slag can be effectively inhibited (the f.CaO in the dephosphorization slag is reduced), the reutilization of the pretreated slag is facilitated, and therefore, a new way of utilizing the high added value of the waste is developed.

Claims (9)

1. The molten iron dephosphorizing agent using converter slag as raw material is characterized by containing the following components,
20-50 of converter slag
15-28 of lime
20-43 of iron oxide
The above are weight percentages.
2. The dephosphorizing agent for molten iron using converter slag as raw material according to claim 1, further comprising one or more of fluorite, soda, limestone in the following weight percentages based on the total amount of the dephosphorizing agent for molten iron:
fluorite is more than 0 and less than or equal to 3
0 is more than soda and less than or equal to 3
Limestone is more than 0 and less than or equal to 3.
3. The dephosphorizing agent for molten iron using converter slag as raw material according to claim 1, wherein CaO/SiO contained in said converter slag22.0 to 4.5.
4. The dephosphorizing agent for molten iron using converter slag as a starting material according to claim 1, wherein P contained in said converter slag2O5≤2.5％。
5. The dephosphorizing agent for molten iron using converter slag as raw material according to claim 1, wherein the content of CaO in lime is not less than 85%.
6. The dephosphorizing agent for molten iron using converter slag as raw material according to claim 1, wherein the iron oxide content in said iron oxide is not less than 70%.
7. The dephosphorizing agent for molten iron using converter slag as raw material according to claim 1, wherein Na in said soda is2CO3The content is more than or equal to 95 percent.
8. The dephosphorizing agent for molten iron using converter slag as raw material according to claim 1, wherein CaF in fluorite2The content is more than or equal to 85 percent.
9. The dephosphorizing agent for molten iron using converter slag as raw material according to claim 1 or 5, wherein said iron oxide is selected from the group consisting of sintered ore and rolled iron sheet, and further selected from the group consisting of converter dust and sintered fly ash.
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CN100447256C (en) * 2006-12-07 2008-12-31 石恩平 Method for making dephosphorization agent from basic skimming
CN102337373A (en) * 2011-11-07 2012-02-01 秦皇岛首秦金属材料有限公司 Using method for recovering refining slag and recycling in converter
CN101560586B (en) * 2009-04-23 2012-03-14 重庆大学 Compound dephosphorization agent with converter slag as raw material and preparing method thereof
CN102719597A (en) * 2012-03-29 2012-10-10 鞍钢股份有限公司 Converter tapping dephosphorization method of interstitial free steel
CN102796840A (en) * 2012-07-11 2012-11-28 攀钢集团研究院有限公司 Coolant for dephosphorizing and extracting vanadium of converter, production method thereof, and method for dephosphorizing and extracting vanadium of converter
CN103170591A (en) * 2013-03-05 2013-06-26 新疆八一钢铁股份有限公司 Production technology for steel ladle and molten steel covering agent
CN103498016A (en) * 2013-10-12 2014-01-08 钢铁研究总院 Dephosphorization agent prepared by taking slag of decarbonization furnace as raw material and molten iron dephosphorization method
CN104498671A (en) * 2014-12-09 2015-04-08 内蒙古包钢钢联股份有限公司 Cold bonding dephosphorization fluxes for steelmaking and preparation method of cold bonding dephosphorization fluxes
CN105349728A (en) * 2015-11-26 2016-02-24 攀钢集团攀枝花钢铁研究院有限公司 Method for simultaneously conducting dephosphorization and vanadium extraction on vanadium-contained molten iron through converter
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CN100447256C (en) * 2006-12-07 2008-12-31 石恩平 Method for making dephosphorization agent from basic skimming
CN101560586B (en) * 2009-04-23 2012-03-14 重庆大学 Compound dephosphorization agent with converter slag as raw material and preparing method thereof
CN102337373A (en) * 2011-11-07 2012-02-01 秦皇岛首秦金属材料有限公司 Using method for recovering refining slag and recycling in converter
CN102719597A (en) * 2012-03-29 2012-10-10 鞍钢股份有限公司 Converter tapping dephosphorization method of interstitial free steel
CN102796840B (en) * 2012-07-11 2014-08-20 攀钢集团研究院有限公司 Coolant for dephosphorizing and extracting vanadium of converter, production method thereof, and method for dephosphorizing and extracting vanadium of converter
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CN103170591A (en) * 2013-03-05 2013-06-26 新疆八一钢铁股份有限公司 Production technology for steel ladle and molten steel covering agent
CN103498016A (en) * 2013-10-12 2014-01-08 钢铁研究总院 Dephosphorization agent prepared by taking slag of decarbonization furnace as raw material and molten iron dephosphorization method
CN104498671A (en) * 2014-12-09 2015-04-08 内蒙古包钢钢联股份有限公司 Cold bonding dephosphorization fluxes for steelmaking and preparation method of cold bonding dephosphorization fluxes
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CN106244760A (en) * 2016-09-07 2016-12-21 攀钢集团攀枝花钢铁研究院有限公司 A kind of vanadium-bearing hot metal is the method for dephosphorization in converter extracting vanadium
CN106282478A (en) * 2016-09-07 2017-01-04 攀钢集团攀枝花钢铁研究院有限公司 A kind of production method of low-phosphorous half steel
CN106244898B (en) * 2016-09-07 2018-05-25 攀钢集团攀枝花钢铁研究院有限公司 A kind of production method of Low-phosphorus Steel
CN107447156A (en) * 2017-08-01 2017-12-08 江油市长祥特殊钢制造有限公司 Hot die steel and its production method
CN107447156B (en) * 2017-08-01 2019-06-04 江油市长祥特殊钢制造有限公司 Hot die steel and its production method
CN108315524A (en) * 2018-02-28 2018-07-24 攀钢集团攀枝花钢铁研究院有限公司 A method of reducing semi-steel making supplementary product onsumption
CN108251590A (en) * 2018-03-14 2018-07-06 攀钢集团攀枝花钢铁研究院有限公司 A kind of method for improving converter lining life
CN108330243A (en) * 2018-03-14 2018-07-27 攀钢集团攀枝花钢铁研究院有限公司 A method of it reducing converter lining and corrodes
CN108315525A (en) * 2018-04-27 2018-07-24 攀钢集团攀枝花钢铁研究院有限公司 semi-steel dephosphorizing method
CN109280745A (en) * 2018-10-31 2019-01-29 首钢集团有限公司 A kind of convertor steelmaking process dephosphorization core-spun yarn
CN111944946A (en) * 2020-08-17 2020-11-17 河北蓝海智投环保科技有限公司 Dedusting ash cold pressing block and preparation method and application thereof
CN111944946B (en) * 2020-08-17 2021-03-23 河北蓝海智投环保科技有限公司 Dedusting ash cold pressing block and preparation method and application thereof
CN112961962A (en) * 2021-02-04 2021-06-15 东北大学 Composite dephosphorizing agent for tapping after furnace, preparation method and application
CN113337664A (en) * 2021-06-11 2021-09-03 华北理工大学 Composite dephosphorization agent based on decarburization slag and preparation method and application thereof
CN113337664B (en) * 2021-06-11 2023-03-07 华北理工大学 Composite dephosphorization agent based on decarburization slag and preparation method and application thereof

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